Method of rapid hair dyeing

ABSTRACT

The present invention relates to a method of hair coloring and bleaching compositions providing a composition comprising i) at least one source of peroxymonocarbonate ions, ii) at least one alkalizing agent, preferably a source of ammonium ions, and iii) at least one radical scavenger, wherein said composition has a pH of up to 9.5, and applying the composition to the hair and retaining on the hair for a period of less than 20 minutes, which provide a high level of lift and lightening and the required dye deposition and grey coverage whilst reducing the concentration of peroxide, the ammonia odor and reducing the hair fiber damage.

FIELD OF THE INVENTION

The present invention relates to a method of rapid bleaching andcolouration of keratinous fibres.

BACKGROUND OF THE INVENTION

The permanent alteration of the colour of keratinous fibres, inparticular human hair, by the application of hair dyes is well known. Inorder to provide the consumer with the hair colour and the intensity ofcolour desired, a very complex chemical process is utilized. Permanenthair dyeing formulations typically comprise oxidative hair dyeprecursors, which can diffuse into the hair through the cuticle and intothe cortex where they can then react with each other and suitableoxidising agents to form the end dye molecules. Due to the large size ofthese resultant molecules they are unable to readily diffuse out of thehair during subsequent washing with water and/or detergents; hencedelivering the consumer-desired permanency of colour. The reactiontypically takes place in an aggressive environment at approximately pH10 in the presence of an alkalizing agent and in the presence of anoxidizing agent. Moreover, the consumer repeats this process regularlyin order to maintain the desired hair colour shade and the intensity ofcolour and to ensure continual, even coverage of the hair includingcoverage of new hair growth.

However, despite the fact that commercial hair dyeing products have beenavailable for many years, the products still exhibit a number ofconsumer-related deficiencies. In particular, the application of hairdye products is still a relatively time consuming process and it maytake the consumer over an hour to mix, apply, wait for the colour todevelop and remove the product; before drying and restyling. Since formost consumers the hair dyeing process is a regular part of their beautyroutine it would be highly desirable if the time required to dye thehair could be reduced whilst still meeting all of the other requirementsof; ease of application, low odour, and especially of course thedelivery of the required hair colour, particularly for consumersrequiring significant changes and/or levels of lift in the resultantcolour.

A number of attempts have been described in the literature to reduce theapplication time required to dye hair, for example by the use ofoxidative hair dye or bleach compositions comprising carbonate. Forexample;

WO01/28508 describes hair dyeing and bleaching compositions comprisingan oxidising agent, hair colouring agents and ammonium carbonate and orcarbamate which provides improved bleaching and colouring with reducedodour and hair damage without the need for buffering agents, pHmodifiers or hair swelling agents. The compositions are applied to thehair for a time period of from 1 to 60 minutes.

FR1592939 describes a hair dyeing composition comprising oxidative dyes,ammonium carbonate and hydrogen peroxide at pH 7-9 which provideseffective dyeing in a fairly short period of time.

EP435012 describes hair-dyeing compositions, which require a shortdyeing time, create little damage to hair, and no irritating odour afterdyeing comprising a carbonate source, a non odour generating alkalihydrogen peroxide and a buffer solution. Similarly, EP1106166 describeshair dye compositions comprising ammonia, carbonate (other than ammoniasalt), transition metal salt and chelating agent which do not give offan irritating odour, have low skin irritation and can change the haircolour into a lighter tone in a short time.

WO04/014328 describes one step hair colouring compositions comprisingperoxide oxidizing agents, specific oxidizing agents and at least onewater soluble carbonate releasing salts which more effectively delivercolour wherein the composition is applied for a period of from 2 to 60minutes.

Other attempted solutions have been described in U.S. Pat. No. 6,703,004which describes hair bleaching compositions comprising an aqueousoxidising agent, persulphate, and a hydrophilic oil, in amountssufficient to provide a mixture containing 3-5% active oxygen, and0.7-1.2 meq/gm alkalinity, wherein the composition is capable ofbleaching the hair in 10 to 30 minutes. Similarly, U.S. Pat. No.6,669,933 describes an aqueous hair colouring composition foroxidatively colouring hair in less than 12 minutes comprising a dye anddeveloper mixture, a free alkalinity concentration of 0.2-0.75 meq/gramand hydrogen peroxide.

US2004/0078906 describes a process for rapid dyeing and decolouration ofkeratin wherein a specific direct dye is applied to the fibres for aleave in time of less than 5 minutes.

Alternative attempts to reduce the application time of hair dyes on headinvolve methods which require short consecutive treatments of haircolourants whereby the colour change is achieved gradually after time.For example WO01/76546 describes a method of colouring hair comprisingthe steps of applying a hair colour altering composition to hair andleaving it on hair for about 0.5 to 15 minutes, wherein this method isrepeated from once a month to about 3 times a day.

US2003/0154561 describes a method of applying an oxidative shampoo for atime period of from 5 seconds to 5 minutes whereby the treatment isrepeated between 2 to 30 times and the time interval between treatmentsis 8 hrs to 30 days. Similarly, US2004/0098814 describes a method ofpermanently whereby the hair is subjected to a number of consecutiveshort treatments whereby the treatment comprises a dye intermediate in ashampoo or conditioner base, a water soluble carbonate releasing saltand a water soluble ammonium salt. US2004/0098816 also describes amethod for the gradual permanent colouring of hair which includessubjecting the hair to a number of treatments having a set time intervalbetween them, wherein the treatment compositions comprise ammoniumcarbonate in combination with a chelant.

However, none of these documents successfully address the problemsassociated with rapid hair colour delivery. In particular, the problemof hair damage resulting from the use of high concentrations of hydrogenperoxide and ammonia to provide the required lift and colour andsimilarly the problem of scalp irritation again typically due to thepresence of a high concentration of hydrogen peroxide and ammonia andalso the high pH value are not satisfactorily resolved with currenttechnologies and marketed products.

Another critical problem with the rapid colour compositions of the priorart is the delivery of the required resultant colour and also theeffective coverage of grey hair; the amount and distribution of whichvaries considerably from consumer to consumer. The prior art not onlydoes not deliver the required shade and depth of colour, but, inparticular, also fails to meet the needs of consumers wishing to lightentheir hair colour by a number of levels of lift. The delivery of suchlightening requires significant bleaching which is currently onlyprovided by compositions comprising high levels of hydrogen peroxide andwhich are utilised over an extended period of time on the hair in orderto provide the consumer with the desired colour outcome. Likewise, theprior art compositions also do not deliver uniform and even colour onthe hair or maintain the initial colour coverage achieved during thepost dyeing washing and drying cycle.

Hence, it would be further desirable to provide the consumer with a haircolourant, providing desired levels of lift and lightening, as well asimproved colour delivery and reduced damage, reduced skin and scalpirritation and low odour which is effective over shorter time periods ofapplication than currently available products and which can be used aspart of the consumer's regular beauty care routine. Moreover, it wouldalso be desirable to provide a rapid colour delivery system whereby thedifficulty in applying the composition onto the hair in a quick butthorough manner is addressed.

It has now been surprisingly found that oxidative hair colouringcompositions comprising an oxidising agent, a source of carbonate ionsand an alkalising agent utilised at pH 9.5 and below provide a rapidlyacting hair bleach or colourant that delivers the required colourrequiring less than 20 minutes development time on the hair of theconsumer, whilst still delivering the required colour as currentlyutilised ammonia/peroxide systems requiring 45 minutes waiting time.Moreover, the method of the present invention reduces damage to thehair, reduces skin and scalp irritation, has low odour and is compatiblewith current dye and dye precursor systems, resulting in improved liftand lightening for blonde shades, excellent dye deposition, uniformityand colour, particularly grey coverage, which is maintained overconsumers wash and styling cycle until the next colouring treatment. Themethod also allows for quick actual application of the compositions tothe hair and minimises staining of the consumers skin, particularlyalong the hair line, whilst delivering the desired colour.

SUMMARY OF THE INVENTION

The present invention relates to a method of oxidative hair colouringand hair bleaching comprising the steps of providing a compositioncomprising i) at least one source of peroxymonocarbonate ions and ii) atleast one source of alkalizing agent, preferably ammonium ions whereinsaid composition has a pH of up to and including 9.5 and then applyingsaid composition to the hair and retaining said composition on the hairfor a time period of less than 20 minutes and subsequently rinsing saidcomposition from the hair.

In a further aspect the present invention relates to the use of acomposition comprising i) at least one source of peroxymonocarbonateions and ii) at least one source of alkalizing agent, preferablyammonium ions wherein said composition has a pH of up to and including9.5 to oxidatively colour or bleach hair in less than 20 minutes.

Another aspect of the present invention relates to a method ofsequential oxidative hair colouring or hair bleaching comprising thesteps of at least two sequential oxidative hair colour or hair bleachingtreatments wherein the time period between each treatment is from 1 dayto 60 days, and wherein each treatment comprises the steps of providinga composition comprising i) at least one source of peroxymonocarbonateions and ii) at least one source of alkalizing agent, preferablyammonium ions wherein said composition has a pH of less than 9.5 andthen applying said composition to the hair and retaining saidcomposition on the hair for a time period of less than 20 minutes andsubsequently rinsing said composition from the hair.

Another aspect of the present invention relates to a method ofpre-treatment of the hair whereby the hair is first applied with apre-treatment composition comprising at least one conditioning agentwhich is retained on the hair prior to the application of the haircolouring or bleaching composition.

DETAILED DESCRIPTION OF THE INVENTION

While the specification concludes with claims, which particularly pointout and distinctly claim the invention, it is believed the presentinvention will be better understood from the following description.

As used herein the term “hair” to be treated may be “living” i.e. on aliving body or may be “non-living” i.e. in a wig, hairpiece or otheraggregation of non-living keratinous fibers. Mammalian, preferably humanhair is preferred. However wool, fur and other keratin containing fibersare suitable substrates for the compositions according to the presentinvention.

All percentages are by weight of the total composition unlessspecifically stated otherwise. When more than one composition are usedduring a treatment, the total weight to be considered is the totalweight of all the compositions applied on the hair simultaneously (i.e.the weight found “on head”) unless otherwise specified. All ratios areweight ratios unless specifically stated otherwise.

Currently marketed hair permanent colourant products typically utilize acombination of an alkaliser system, dye precursors and an oxidant todeliver the desired hair colour to the consumer. The alkaliser istypically ammonia or an alkanolamine, such as monoethanolamine and theoxidant is typically hydrogen peroxide or a solid form of hydrogenperoxide. The final hair colour which is delivered to the consumer is acombination of the result of the underlying bleaching of the melaninpigment in the hair fibre and the delivery of the coloured dyechromophore moieties which are either preformed, that is direct dyes orare formed by oxidatization of the dye precursors within the hair fibre.

The optimal pH for such systems is typically about pH 10.0. This high pHis necessary in order to produce a sufficient concentration of theperhydroxy anion (HOO—) to give the desired bleaching of the melanin. Ithas been found that below pH 9.5 the concentration of this species isless than 0.01% of the added hydrogen peroxide concentration (pKa=11.6)and the amount of melanin bleaching drops dramatically and is henceinsufficient to give the desired final colour.

However, as discussed herein above, compositions having a high pH causemany of the disadvantages noted by consumers for these colourantsystems. In particular, the level of the volatile ammonia increases athigh pH (above pH 9.5) giving increased unpleasant odour. Also, someconsumers suffer from skin and scalp irritation. Furthermore, reactivespecies including the perhydroxy anions react with the hair fibreresulting in significant fibre damage. One consequence of thisreactivity is that the hydrophilicity of the hair fibres issignificantly increased and this causes an increase in the forcerequired to comb the hair compared with hair that has not been coloured.Moreover, the higher forces that are exerted during combing and stylingfurther result in increased fibre damage to the hair fibres.

It has now been surprisingly found that a method of colouring andbleaching hair whereby a composition comprising the combination of atleast one source of peroxymonocarbonate ions, preferably formed insitufrom a source of hydrogen peroxide and a carbonate ion source and atleast one source of alkalizing agents, and preferably at least onesource of radical scavenger, (as defined hereinafter), and preferablydyes and/or dye precursors, at a pH of up to and including 9.5,preferably 7.5 to 9.5, is applied to the hair of the consumer for a timeperiod of less than 20 minutes can deliver improvements to the desiredhair colour results, whilst considerably reducing the odour, skin andscalp irritation and damage to the hair fibres.

Whilst not wishing to be bound by theory, it is believed that in thepresent invention the key species responsible for the bleaching of themelanin, namely the peroxymonocarbonate ion (—OC(O)OOH), decomposes atpH values above 9.5 to form oxygen and the hydrogen carbonate ion. At pHvalues below 7.5 the hydrogen carbonate ion decomposes to form carbondioxide and water. At pH values of 9.0 the bleaching of the melanin andthe final colour observed is at an optimal level. Thus surprisingly thepresent invention allows for the delivery of improved lift, in otherwords hair lightening which is a highly desirable consumer need.Furthermore, compositions having a pH lower than 9.5 have the benefitthat not only the unpleasant ammonia odour is significantly reduced butalso the hair fibre damage is reduced. Moreover, due to the kinetics ofthe carbonate system the compositions require only a short developmenttime on the hair of the consumers head of up to about 20 minutes inorder to deliver improved uniform colour which is retained during thewash and styling cycle.

The compositions according to the present invention thus comprise asource of peroxymonocarbonate ions. These ions are typically formedinsitu from the reaction between a source of hydrogen peroxide andcarbonate ion. Consequently, the compositions according to the presentinvention comprise or are used in combination with a composition thatcomprises at least one source of an oxidizing agent. Preferred oxidizingagents for use herein are water-soluble peroxygen oxidizing agents.“Water-soluble” as defined herein means that in standard condition atleast 0.1 g, preferably 1 g, more preferably 10 g of said oxidizingagent can be dissolved in 1 liter of deionized water. The oxidizingagents are valuable for the initial solubilisation and decolorisation ofthe melanin (bleaching) and accelerate the oxidation of the oxidativedye precursors (oxidative dyeing) in the hair shaft.

Any oxidizing agent known in the art may be utilized in the presentinvention. Preferred water-soluble oxidizing agents are inorganicperoxygen materials capable of yielding hydrogen peroxide in an aqueoussolution. Water-soluble peroxygen oxidizing agents are well known in theart and include hydrogen peroxide, inorganic alkali metal peroxides suchas sodium periodate and sodium peroxide and organic peroxides such asurea peroxide, melamine peroxide, and inorganic perhydrate saltbleaching compounds, such as the alkali metal salts of perborates,percarbonates, perphosphates, persilicates, persulphates and the like.These inorganic perhydrate salts may be incorporated as monohydrates,tetrahydrates etc. Alkyl and aryl peroxides and or peroxidases may alsobe used. Mixtures of two or more such oxidizing agents can be used ifdesired. The oxidizing agents may be provided in aqueous solution or asa powder which is dissolved prior to use. Preferred for use in thecompositions according to the present invention are hydrogen peroxide,percarbonate (which may be used to provide a source of both oxidizingagent and carbonate ions), persulphates and combinations thereof.

According to the present invention the compositions comprise from about0.1% to about 10% by weight, preferably from about 1% to about 7% byweight, and most preferably from about 2% to about 5% by weight of anoxidizing agent.

Carbonate Ion Source

According to the present invention the compositions thus also compriseat least a source of carbonate ions or carbamate ions or hydrocarbonateions or any mixture thereof. Any source of these ions may be utilized.Suitable sources for use herein include sodium, potassium, guanidine,arginine, lithium, calcium, magnesium, barium, ammonium salts ofcarbonate, carbamate and hydrocarbonate ions and mixtures thereof suchas sodium carbonate, sodium hydrogen carbonate, potassium carbonate,potassium hydrogen carbonate, guanidine carbonate, guanidine hydrogencarbonate, lithium carbonate, calcium carbonate, magnesium carbonate,barium carbonate, ammonium carbonate, ammonium hydrogen carbonate andmixtures thereof. Percarbonate salts may also be utilized to provideboth the source of carbonate ions and oxidizing agent. Preferred sourcesof carbonate ions, carbamate and hydrocarbonate ions are sodium hydrogencarbonate, potassium hydrogen carbonate, ammonium carbamate and mixturesthereof.

The compositions of the present invention may comprise from about 0.1%to about 15%, preferably from about 0.1% to about 10% by weight, morepreferably from about 1% to about 8% by weight of the carbonate ion.Preferably, if present, the ammonium ions and carbonate ions are presentin the composition at a weight ratio of from 3:1 to 1:10, preferably 2:1to 1:5. In a particularly preferred embodiment of the present inventionthe ammonium ions and carbonate ion sources are provided by a singlesource such as ammonium carbonate, ammonium hydrogen carbonate, ammoniumhydrocarbonate or mixtures thereof.

Source of Alkalizing Agent

According to the present invention the composition also comprises atleast one source of alkalizing agent, preferably a source of ammoniumions and or ammonia. Any agent known in the art may be used such asalkanolamides for example monoethanolamine, diethanolamine,triethanolamine, monopropanolamine, dipropanolamine, tripropanolamine,2-amino-2-methyl-1,3-propanediol, 2-amino-2-methyl-1-propanol, and2-amino-2-hydroxymethyl-1,3-propanediol and guanidium salts.Particularly, preferred alkalizing agents are those which provide asource of ammonium ions. Any source of ammonium ions is suitable for useherein. Preferred sources include ammonium chloride, ammonium sulphate,ammonium nitrate, ammonium phosphate, ammonium acetate, ammoniumcarbonate, ammonium hydrogen carbonate, ammonium carbamate, ammoniumhydroxide, percarbonate salts, ammonia and mixtures thereof.Particularly preferred are ammonium carbonate, ammonium carbamate,ammonia and mixtures thereof

The compositions of the present invention may comprise from about 0.1%to about 10% by weight, preferably from about 0.5% to about 6%, mostpreferably from about 1% to about 3% of an alkalizing agent, preferablyammonium ions.

pH

According to the method of the present invention the compositions of thepresent invention have a pH up to and including pH 9.5. Preferably, thecompositions of the present invention have a pH of from about 9.5 toabout 7.5, more preferably from about 9.5 to about 8.4 and mostpreferably from about 9.4 to about 8.5 and even more preferably about pH9.0.

Preferably the compositions of the present invention are prepared suchthat prior to application to the hair fibres the pH of the compositionis no greater than about pH 9.5. However, in another embodiment of thepresent invention the compositions may be formulated such that the pH isup to 9.5 during the time period of application of the composition tothe hair fibres prior to removal therefrom. Preferably, the pH is up toabout 9.5 for at least 50% of the time period, preferably at least 70%,more preferably at least 80%, most preferably at least 90% of the timeperiod of application of the composition to the hair.

The pH of the compositions can be determined by using either a MettlerToledo MP220 or a MP225 pH equipment, fitted with a standard laboratorypH electrode. The equipment is calibrated before each use using standardcalibration buffers and using standard calibration procedure.

It is known that for good lightening and good colour formation that thefinal formulation should have a good buffering capacity or reservealkalinity (the ability of the system to resist the pH shift that wouldotherwise be caused by addition of acid). The reserve alkalinity ismeasured using a Mettler DL70 auto-titrator with 0.1N methanolichydrochloric acid being added to 0.7 mL of thoroughly mixed colourantproduct in 50 mL of methanol. The electrode is calibrated and then usedto measure the amount of acid required to reach the sharpest end pointtriggered by a rapid change in pH. Using this method it has beendetermined that a reserve alkalinity of at least 0.2 ml of 0.1N ofethanolic hydrochloric acid and preferably above 0.4 is required forgood lightening and colouring. Suitable buffering systems includeammonia/ammonium acetate mixtures, monoethanolamine tetrasodiumpyrophosphate, isopropanolamine, benzoic acid

Additional Components

The compositions of the present invention may further compriseadditional ingredients which include, but are not limited to, hairdyeing agents such as oxidative dye precursors, non-oxidative dyes,thickeners, solvents, enzymes, surfactants, conditioning agents,carriers, antioxidants, stabilizers, chelants, perming actives, perfume,reducing agents (thiolactic acid), hair swelling agents, hydrophobicoils such as coconut oil, mineral oil, isopropyl myristrate, linseed oiland octyl palmitate and/or polymers. Some of these additional componentsare detailed hereafter.

Hair Dyes

The hair colouring compositions of the present invention are preferablyhair colouring compositions which comprise oxidative dyeingcompositions. Such compositions comprise oxidative hair dye precursors(also known as primary intermediates) that will deliver a variety ofhair colors to the hair. These small molecules are activated by theoxidizing agent and react with further molecules to form a largercolored complex in the hair shaft.

The precursors can be used alone or in combination with otherprecursors, and one or more can be used in combination with one or morecouplers. Couplers (also known as color modifiers or secondaryintermediates) are generally colorless molecules that can form colors inthe presence of activated precursors, and are used with other precursorsor couplers to generate specific color effects or to stabilize thecolor.

The choice of precursors and couplers will be determined by the color,shade and intensity of coloration that is desired. The precursors andcouplers can be used herein, singly or in combination, to provide dyeshaving a variety of shades ranging from ash blonde to black.

These compounds are well known in the art, and include aromaticdiamines, aminophenols, and their derivatives (a representative but notexhaustive list of oxidation dye precursor can be found in Sagarin,“Cosmetic Science and Technology”, “Interscience, Special Edn. Vol. 2pages 308 to 310). It is to be understood that the precursors detailedbelow are only by way of example and are not intended to limit thecompositions and processes herein. These are:

p-phenylenediamine derivatives, e.g. benzene-1,4-diamine (commonly knownas p-phenylenediamine), 2-methyl-benzene-1,4-diamine,2-chloro-benzene-1,4-diamine, N-phenyl-benzene-1,4-diamine,N-(2-ethoxyethyl)benzene-1,4-diamine,2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol, (commonly known asN,N-bis(2-hydroxyethyl)-p-phenylenediamine)(2,5-diamino-phenyl)-methanol, 1-(2′-Hydroxyethyl)-2,5-diaminobenzene,2-(2,5-diamino-phenyl)-ethanol, N-(4-aminophenyl)benzene-1,4-diamine,2,6-dimethyl-benzene-1,4-diamine, 2-isopropyl-benzene-1,4-diamine,1-[(4-aminophenyl)amino]-propan-2-ol, 2-propyl-benzene-1,4-diamine,1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]propan-2-ol,N⁴,N⁴,2-trimethylbenzene-1,4-diamine, 2-methoxy-benzene-1,4-diamine,1-(2,5-diaminophenyl)ethane-1,2-diol, 2,3-dimethyl-benzene-1,4-diamine,N-(4-amino-3-hydroxy-phenyl)-acetamide, 2,6-diethylbenzene-1,4-diamine,2,5-dimethylbenzene-1,4-diamine, 2-thien-2-ylbenzene-1,4-diamine,2-thien-3-ylbenzene-1,4-diamine, 2-pyridin-3-ylbenzene-1,4-diamine,1,1′-biphenyl-2,5-diamine, 2-(methoxymethyl)benzene-1,4-diamine,2-(aminomethyl)benzene-1,4-diamine, 2-(2,5-diaminophenoxy)ethanol,N-[2-(2,5-diaminophenoxy)ethyl]-acetamide,N,N-dimethylbenzene-1,4-diamine, N,N-diethylbenzene-1,4-diamine,N,N-dipropylbenzene-1,4-diamine, 2-[(4-aminophenyl)(ethyl)amino]ethanol,2-[(4-amino-3-methyl-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,N-(2-methoxyethyl)-benzene-1,4-diamine,3-[(4-aminophenyl)amino]propan-1-ol,3-[(4-aminophenyl)-amino]propane-1,2-diol,N-{4-[(4-aminophenyl)amino]butyl}benzene-1,4-diamine, and2-[2-(2-{2-[(2,5-diaminophenyl)-oxy]ethoxy}ethoxy)ethoxy]benzene-1,4-diamine;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; p-aminophenol derivativessuch as: 4-amino-phenol (commonly known as p-aminophenol),4-methylamino-phenol, 4-amino-3-methyl-phenol,4-amino-2-hydroxymethyl-phenol, 4-amino-2-methyl-phenol,4-amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene,4-amino-2-methoxymethyl-phenol, 5-amino-2-hydroxy-benzoic acid,1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol,4-amino-2-(2-hydroxy-ethyl)-phenol, 4-amino-3-(hydroxymethyl)phenol,4-amino-3-fluoro-phenol, 4-amino-2-(aminomethyl)-phenol,4-amino-2-fluoro-phenol; 1-Hydroxy-2,4-diaminobenzene;1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene; 2,4-Diamino-5-methylphenetol;o-phenylenediamine derivatives such as: 3,4-Diaminobenzoic acid andsalts thereof; o-aminophenol derivatives such as: 2-amino-phenol(commonly known as o-aminophenol), 2,4-diaminophenol,2-amino-5-methyl-phenol, 2-amino-6-methyl-phenol,N-(4-amino-3-hydroxy-phenyl)-acetamide, and 2-amino-4-methyl-phenol; andheterocyclic derivatives such as: pyrimidine-2,4,5,6-tetramine (commonlyknown as 2,4,5,6-tetraaminopyridine), 1-methyl-1H-pyrazole-4,5-diamine,2-(4,5-diamino-1H-pyrazol-1-yl)ethanol,N²,N²-dimethyl-pyridine-2,5-diamine,2-[(3-amino-6-methoxypyridin-2-yl)amino]ethanol,6-methoxy-N²-methyl-pyridine-2,3-diamine,2,5,6-triaminopyrimidin-4(1H)-one, pyridine-2,5-diamine,1-isopropyl-1H-pyrazole-4,5-diamine,1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine,1-(benzyl)-1H-pyrazole-4,5-diamine,1-(4-chlorobenzyl)-1H-pyrazole-4,5-diamine,pyrazolo[1,5-a]-pyrimidine-3,7-diamine,5,6,7-trimethylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,7-methylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2,5,6,7-teramethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-tert-butylpyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,5,7-di-trifluoromethyl-pyrazolo[1,5-a]pyrimidin-3-ylamine hydrochloride,2-methylpyrazolo[1,5-a]pyrimidin-3,7-diamine hydrochloride;4-Hydroxy-2,5,6-triaminopyrimidine;1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and1-Hydroxyethyl-4,5-diaminopyrazole sulphate.

Additional developers include N-(3-furylmethyl)benzene-1,4-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(2-furylmethyl)benzene-1,4-diamine;N-Thiophen-2-ylmethyl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-(6-Methyl-pyridin-2-yl)-benzene-1,4-diamine;2-Pyridin-2-yl-benzene-1,4-diamine;2-[3-(4-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;2-[3-(3-Amino-phenylamino)-propenyl]-benzene-1,4-diamine;3-(2,5-Diamino-phenyl)-N-ethyl-acrylamide;2-Thiazol-2-yl-benzene-1,4-diamine; 4-Hydroxy-benzoic acid(2,5-diamino-benzylidene)-hydrazide; 3′-Fluoro-biphenyl-2,5-diamine;2-Propenyl-benzene-1,4-diamine; 2′-Chloro-biphenyl-2,5-diamine;N-Thiophen-3-ylmethyl-benzene-1,4-diamine;N-(3-furylmethyl)benzene-1,4-diamine; 4′-Methoxy-biphenyl-2,5-diamine;N-(4-Amino-benzyl)-benzene-1,4-diamine;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; Biphenyl-2,4,4′-triaminehydrochloride; 5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diaminehydrochloride; 5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;4-Amino-2-propylaminomethyl-phenol; hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamide;hydrochloride; 4-Amino-2-(isopropylamino-methyl)-phenol; hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride hydrochloride;5-Phenylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;4-Thiophen-3-yl-benzene-1,3-diamine; hydrochloride;2′,4′-Diamino-biphenyl-4-ol; hydrochloride;5-Cyclobutylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol;hydrochloride; 2′,4′-Diamino-biphenyl-4-ol hydrochloride;Biphenyl-2,4,4′-triamine;5-(4-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;2-[4-Amino-2-(3,5-diamino-benzylamino)-phenoxy]-ethanol hydrochloride;5-Allylaminomethyl-benzene-1,3-diamine hydrochloride;5-(3-Amino-phenyl)aminomethyl-benzene-1,3-diamine hydrochloride;N-(4-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-Benzyl-benzene-1,3-diamine hydrochloride;3-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-(2-Amino-benzyl)-benzene-1,3-diamine hydrochloride;N-(4-Methoxy-benzyl)-benzene-1,3-diamine hydrochloride;N-Furan-2-ylmethyl-benzene-1,3-diamine hydrochloride;2-[(3-Amino-phenylamino)-methyl]-phenol hydrochloride;N-Thiophen-2-ylmethyl-benzene-1,3-diamine hydrochloride;N-Benzo[1,3]dioxol-5-ylmethyl-benzene-1,3-diamine hydrochloride;N-[4-Amino-2-(2-hydroxy-ethyl)-2H-pyrazol-3-yl]-3-(5-amino-2-hydroxy-phenyl)-acrylamidehydrochloride; 4-Amino-2-propylaminomethyl-phenol; hydrochloride;4-Amino-2-(isopropylamino-methyl)-phenol hydrochloride;4-Amino-2-[(2-hydroxy-5-nitro-phenylamino)-methyl]-phenol hydrochloride;2-Methyl-5-[(1-H-pyrrol-2-ylmethyl)-amino]-phenol;5-[(Furan-2-ylmethyl)-amino]-2-methyl-phenol;5-Isopropylamino-2-methyl-phenol; 5-Cyclobutylamino-2-methyl-phenol;4-Amino-2-(pyridin-3-ylaminomethyl)-phenol; and5-Cyclobutylamino-2-methyl-phenol.

Preferred developers include: p-phenylenediamine derivatives such as:2-methyl-benzene-1,4-diamine; benzene-1,4-diamine;1-(2,5-diamino-phenyl)-ethanol; 2-(2,5-diamino-phenyl)-ethanol;N-(2-methoxyethyl)benzene-1,4-diamine;2-[(4-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol;1-(2,5-diaminophenyl)ethane-1,2-diol;1-(2′-Hydroxyethyl)-2,5-diaminobenzene;1,3-Bis(N(2-Hydroxyethyl)-N-(4-amino-phenyl)amino)-2-propanol;2,2′-[1,2-Ethanediyl-bis-(oxy-2,1-ethanediyloxy)]-bis-benzene-1,4-diamine;N,N-Bis(2-hydroxyethyl)-p-phenylinediamine; and mixtures thereof;p-aminophenol derivatives such as: 4-amino-phenol, 4-methylamino-phenol,4-amino-3-methyl-phenol, 4-amino-2-methoxymethyl-phenol;1-(5-amino-2-hydroxy-phenyl)-ethane-1,2-diol;1-Hydroxy-2,4-diaminobenzene; 1-(2′-Hydroxyethyloxy)-2,4-diaminobenzene;4-Amino-2-aminomethylphenol; 2,4-Diamino-5-methylphenetol;4-Amino-1-hydroxy-2-(2′-hydroxyethylaminomethyl)benzene;1-methoxy-2-amino-4-(2′hydroxyethylamino)-benzene; 5-aminosalicylic acidand salts thereof; and mixtures thereof; o-phenylenediamine derivativessuch as: 3,4-Diaminobenzoic acid and salts thereof; o-aminophenolderivatives such as: 2-amino-phenol, 2-amino-5-methyl-phenol,2-amino-6-methyl-phenol, N-(4-amino-3-hydroxy-phenyl)-acetamide;2-amino-4-methyl-phenol; and mixtures thereof; and heterocyclicderivatives such as: pyrimidine-2,4,5,6-tetramine;1-methyl-1H-pyrazole-4,5-diamine;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol;1-(4-methylbenzyl)-1H-pyrazole-4,5-diamine;1-(benzyl)-1H-pyrazole-4,5-diamine; N²,N²-dimethyl-pyridine-2,5-diamine;4-Hydroxy-2,5,6-triaminopyrimidine;1-(2′hydroxyethyl)-amino-3,4-methylene dioxybenzene; and1-Hydroxyethyl-4,5-diaminopyrazole sulphate; and mixtures thereof.

More preferred developers include: 2-methyl-benzene-1,4-diamine;benzene-1,4-diamine; N,N-Bis(2-hydroxyethyl)-p-phenylenediamine;4-amino-phenol; 4-methylamino-phenol; 4-amino-3-methyl-phenol;1-Hydroxy-2,4-diaminobenzene; 2-amino-phenol; 2-amino-5-methyl-phenol;2-amino-6-methyl-phenol; 1-methyl-1H-pyrazole-4,5-diamine;1-Hydroxyethyl-4,5-diaminopyrazole sulphate;2-(4,5-diamino-1H-pyrazol-1-yl)ethanol; and mixtures thereof.

Suitable couplers for use in the compositions described herein include,but are not limited to: phenols, resorcinol and naphthol derivativessuch as: naphthalene-1,7-diol, benzene-1,3-diol,4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol,2-methyl-benzene-1,3-diol, 7-amino-4-hydroxy-naphthalene-2-sulfonicacid, 2-isopropyl-5-methylphenol,1,2,3,4-tetrahydro-naphthalene-1,5-diol, 2-chloro-benzene-1,3-diol,4-hydroxy-naphthalene-1-sulfonic acid, benzene-1,2,3-triol,naphthalene-2,3-diol, 5-dichloro-2-methylbenzene-1,3-diol,4,6-dichlorobenzene-1,3-diol, 2,3-dihydroxy-[1,4]naphthoquinone; and1-Acetoxy-2-methylnaphthalene; m-phenylenediamines such as:2,4-diaminophenol, benzene-1,3-diamine, 2-(2,4-diamino-phenoxy)-ethanol,2-[(3-amino-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-methyl-benzene-1,3-diamine,2-[[2-(2,4-diamino-phenoxy)-ethyl]-(2-hydroxy-ethyl)-amino]-ethanol,4-{3-[(2,4-diaminophenyl)oxy]-propoxy}benzene-1,3-diamine,2-(2,4-diamino-phenyl)-ethanol,2-(3-amino-4-methoxy-phenylamino)-ethanol,4-(2-amino-ethoxy)-benzene-1,3-diamine, (2,4-diamino-phenoxy)-aceticacid, 2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol,4-ethoxy-6-methyl-benzene-1,3-diamine,2-(2,4-diamino-5-methyl-phenoxy)-ethanol,4,6-dimethoxy-benzene-1,3-diamine,2-[3-(2-hydroxy-ethylamino)-2-methyl-phenylamino]-ethanol,3-(2,4-diamino-phenoxy)-propan-1-ol, N-[3-(dimethylamino)phenyl]urea,4-methoxy-6-methylbenzene-1,3-diamine,4-fluoro-6-methylbenzene-1,3-diamine,2-({3-[(2-hydroxyethyl)amino]-4,6-dimethoxyphenyl}-amino)ethanol,3-(2,4-diaminophenoxy)-propane-1,2-diol,2-[2-amino-4-(methylamino)-phenoxy]ethanol,2-[(5-amino-2-ethoxy-phenyl)-(2-hydroxy-ethyl)-amino]-ethanol,2-[(3-aminophenyl)amino]ethanol,2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;N-(2-aminoethyl)benzene-1,3-diamine,4-{[(2,4-diamino-phenyl)oxy]methoxy}-benzene-1,3-diamine,1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and2,4-dimethoxybenzene-1,3-diamine; m-aminophenols such as:3-amino-phenol, 2-(3-hydroxy-4-methyl-phenylamino)-acetamide,2-(3-hydroxy-phenylamino)-acetamide, 5-amino-2-methyl-phenol,5-(2-hydroxy-ethylamino)-2-methyl-phenol, 5-amino-2,4-dichloro-phenol,3-amino-2-methyl-phenol, 3-amino-2-chloro-6-methyl-phenol,5-amino-2-(2-hydroxy-ethoxy)-phenol,2-chloro-5-(2,2,2-trifluoro-ethylamino)-phenol,5-amino-4-chloro-2-methyl-phenol, 3-cyclopentylamino-phenol,5-[(2-hydroxyethyl)amino]-4-methoxy-2-methylphenol,5-amino-4-methoxy-2-methylphenol, 3-(dimethylamino)phenol,3-(diethylamino)phenol, 5-amino-4-fluoro-2-methylphenol,5-amino-4-ethoxy-2-methylphenol, 3-amino-2,4-dichloro-phenol,3-[(2-methoxyethyl)amino]phenol, 3-[(2-hydroxyethyl)amino]phenol,5-amino-2-ethyl-phenol, 5-amino-2-methoxyphenol,5-[(3-hydroxy-propyl)amino]-2-methylphenol,3-[(3-hydroxy-2-methylphenyl)-amino]propane-1,2-diol,3-[(2-hydroxyethyl)amino]-2-methylphenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)amino-benzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene; and heterocyclic derivativessuch as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one,6-methoxyquinolin-8-amine, 4-methylpyridine-2,6-diol,2,3-dihydro-1,4-benzodioxin-5-ol, 1,3-benzodioxol-5-ol,2-(1,3-benzodioxol-5-ylamino)ethanol, 3,4-dimethylpyridine-2,6-diol,5-chloropyridine-2,3-diol, 2,6-dimethoxypyridine-3,5-diamine,1,3-benzodioxol-5-amine,2-{[3,5-diamino-6-(2-hydroxy-ethoxy)-pyridin-2-yl]oxy}-ethanol,1H-indol-4-ol, 5-amino-2,6-dimethoxypyridin-3-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol,6-bromo-1,3-benzodioxol-5-ol, 2-aminopyridin-3-ol, pyridine-2,6-diamine,3-[(3,5-diaminopyridin-2-yl)oxy]propane-1,2-diol,5-[(3,5-diaminopyridin-2-yl)oxy]pentane-1,3-diol, 1H-indole-2,3-dione,indoline-5,6-diol, 3,5-dimethoxypyridine-2,6-diamine,6-methoxypyridine-2,3-diamine; 3,4-dihydro-2H-1,4-benzoxazin-6-amine;4-hydroxy-N-methylindole, 1H-5-methylpyrazol-5-one,1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole, 2,6-dihydroxypyridine,2,6-dihydroxy-3,4-dimethylpyridine,5-methylpyrazolo[5,1-e]-1,2,3-triazole,5-methyl-6-chloropyrazolo[5,1-e]-1,2,3,-triazole,5-phenylpyrazolo[5,1-e]-1,2,3-triazole and its addition salts,1H-2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole tosylate,7,8-dicyano-4-methylimidazolo-[3,2-a]imidazole,2,7-dimethylpyrazolo[1,5-a]pyrimidin-5-one,2,5-dimethylpyrazolo[1,5-a]pyrimidin-7-one, and2-methyl-5-methoxymethyl-pyrazolo[1,5-a]pyrimidin-7-one;6-Hydroxybenzomorpholine; and 3-Amino-2-methylamino-6-methoxypyridine;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one.

Preferred couplers include: phenol, resorcinol, and naphthol derivativessuch as: naphthalene-1,7-diol, benzene-1,3-diol,4-chlorobenzene-1,3-diol, naphthalen-1-ol, 2-methyl-naphthalen-1-ol,naphthalene-1,5-diol, naphthalene-2,7-diol, benzene-1,4-diol,2-methyl-benzene-1,3-diol, and 2-isopropyl-5-methylphenol;1,2,4-Trihydroxybenzene; 1-Acetoxy-2-methylnaphthalene; and mixturesthereof; m-phenylenediamine derivatives such as: benzene-1,3-diamine,2-(2,4-diamino-phenoxy)-ethanol,4-{3-[(2,4-diaminophenyl)oxy]-propoxy}benzene-1,3-diamine,2-(3-amino-4-methoxy-phenylamino)-ethanol,2-[2,4-diamino-5-(2-hydroxy-ethoxy)-phenoxy]-ethanol, and3-(2,4-diamino-phenoxy)-propan-1-ol;2,4-Diamino-5-(2′-hydroxyethyloxy)toluene; N,N-Dimethyl-3-ureidoaniline;2,4-Diamino-5-fluorotoluenesulfatehydrate;1-methyl-2,6-bis(2-hydroxyethylamino)benzene; and mixtures thereof;m-aminophenol derivatives such as: 3-amino-phenol,5-amino-2-methyl-phenol, 5-(2-hydroxy-ethylamino)-2-methyl-phenol, and3-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;1-Hydroxy-3-amino-2,4-dichlorobenzene;1,3-Bis-(2,4-Diaminophenoxy)propane;1-Hydroxy-2-methyl-5-amino-6-chlorobenzene;5-Amino-4-chloro-2-methylphenol; and mixtures thereof; and heterocyclicderivatives such as: 3,4-dihydro-2H-1,4-benzoxazin-6-ol,4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one, 1,3-benzodioxol-5-ol,1,3-benzodioxol-5-amine, 1H-indol-4-ol, 1H-indole-5,6-diol,1H-indol-7-ol, 1H-indol-5-ol, 1H-indol-6-ol, 1H-indole-2,3-dione,pyridine-2,6-diamine, 2-aminopyridin-3-ol, 4-hydroxy-N-methylindole,1H-5-methylpyrazol-5-one, 1-phenyl-3-methylpyrazol-5-one,2,6-dimethylpyrazolo[1,5-b]-1,2,4-triazole,2,6-dimethyl[3,2-c]-1,2,4-triazole,6-methylpyrazolo-[1,5-a]benzimidazole; 2,6-dihydroxypyridine;2,6-dihydroxy-3,4-dimethylpyridine; 6-Hydroxybenzomorpholine;2,6-Dihydroxy-3,4-dimethylpyridine; 3,5-Diamino-2,6-dimethoxypyridine;3-Amino-2-methylamino-6-methoxypyridine;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

More preferred couplers include: benzene-1,3-diol;4-chlorobenzene-1,3-diol; 2-methyl-benzene-1,3-diol;benzene-1,3-diamine; 3-amino-phenol; 5-amino-2-methyl-phenol;1-Methyl-2-hydroxy-4-(2′-hydroxyethyl)aminobenzene;4-methyl-2-phenyl-2,4-dihydro-3H-pyrazol-3-one; 2-aminopyridin-3-ol;1-phenyl-3-methylpyrazol-5-one;1-Phenyl-3-methyl-5-pyrazolone-2,4-dihydro-5,2-phenyl-3H-pyrazole-3-one;and mixtures thereof.

Particularly preferred dyes for use herein include p-phenylene diamine,p-aminophenol, o-aminophenol, 2,5-diaminotoluene sulphate,p-methylaminophenol, N,N-bis-hydroxyethyl-p-phenylene diamine sulphate,4-amino-2,6-dichlorophenol, m-aminophenol, 4-amino-20 hydroxytoluene,resorcinol, methylresorcinol, napthol, 2-amino-3-hydroxy pyridine,2-amino-4-hydroxyethylamino anisole sulphate,2-methyl-5-hydroxyethylaminophenol, m-phenylenediamine sulphate,1-phenyl-3-methyl-5-pyrazolone, 1-hydroxyethyl-4,5-diamino pyrazolesulphate, 1-acetoxy-2-methylnapthalene and mixtures thereof.

The hair colouring compositions of the present invention may include nonoxidative hair dyes i.e. direct dyes which may be used alone or incombination with the above described oxidative dyes. Suitable directdyes include azo or anthraquinone dyes and nitro derivatives of thebenzene series and or melanin precursors and mixtures thereof. Suchdirect dyes are particularly useful to deliver shade modification orhighlights. In fact any molecule having the ability to impart a colourto the hair can be used. Of particluar importance in this respect aremolecules containing either one or more of the following moieties:indigoids, polymethines, phthalocyanines, and aryl carboniums. These andother materials capable of imparting colour, as described in “ChromicPhenomena” by P. Bamfield (ISBN 0-85404-474-4, incorporated byreference) can all find application in the present invention. Of thesematerials, the preferred dyes are those disclosed in US2004/0078906 andof particular preference are the cationic azo dyes.

The hair dye compositions of the present invention will generallycomprise from about 0.001% to about 10% of dyes. For examplecompositions providing low intensity dyeing such as natural blond tolight brown hair shades generally comprise from about 0.001% to about5%, preferably from about 0.1% to about 2%, more preferably from about0.2% to about 1% by weight of dyeing composition of precursors andcouplers. Darker shades such as browns and black typically comprise from0.001% to about 10% by weight, preferably from about 0.05% to about 7%by weight, more preferably form about 1% to about 5% of precursors andcouplers.

Radical Scavenger

According to the present invention the compositions may further comprisea source of radical scavenger. As used herein the term radical scavengerrefers to a species that can react with a carbonate radical to convertthe carbonate radical by a series of fast reactions to a less reactivespecies, i.e. a carbonate radical scavenger.

Whilst not being bound by theory, it is believed that the ability of theradical scavenger to convert the carbonate radical (as describedhereinabove) is dependant upon the energy of the charge transferreaction as shown below: (The calculation of the energy of the chargetransfer reaction is detailed hereinafter.)Scavenger+CO₃*⁻→Scavenger*⁺+CO₃ ²⁻wherein the energy of the reaction is defined by:—ΔH_(r=)ΔH_(f)(products)−ΔH_(f)(reactants)=ΔH_(f)(Scavenger*⁺)+ΔH_(f)(CO₃²⁻)−ΔH_(f)(Scavenger)−ΔH_(f)(CO₃*⁻)

According to the present invention radical scavengers suitable for useherein have an energy of reaction of from about 0 kcal/mol to 14kcal/mol, preferably from about 1.5 kcal/mol to 9 kcal/mol.

Suitable radical scavengers for use herein include compounds accordingto the general formula:R¹—Y—C(H)(R³)—R⁴—(C(H)(R⁵)—Y—R⁶)_(n)   (I)wherein Y is NR², O, or S, preferably NR², n is 0 to 2, and wherein R⁴is monovalent or divalent and is selected from: (a) substituted orunsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (b) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (c) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; the systems of(a), (b) and (c) comprising from 1 to 12 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; and wherein R⁴ can beconnected to R³ or R⁵ to create a 5, 6 or 7 membered ring; and whereinR¹, R², R³, R⁵, and R⁶ are monovalent and are selected independentlyfrom: (a), (b) and (c) described herein above, or H.

Preferably, R⁴ is selected from: (a) substituted or unsubstituted,straight or branched, alkyl, heteroalkyl, aliphatic, heteroaliphatic, orheteroolefinic systems, (b) substituted or unsubstituted, mono- orpoly-cyclic aliphatic, aryl, or heterocyclic systems, or (c) substitutedor unsubstituted, mono-, poly-, or per-fluoro alkyl systems; morepreferably R⁴ is selected from (a) substituted or unsubstituted,straight or branched, alkyl, heteroalkyl, aliphatic, or heteroaliphaticsystems, (b) substituted or unsubstituted, aryl, or heterocyclicsystems, or (c) substituted or unsubstituted, mono-, poly-, orper-fluoro alkyl systems; more preferably substituted or unsubstituted,straight or branched, alkyl, or heteroalkyl systems.

Preferably, the R⁴ systems of (a), (b), and (c), described herein above,comprise from 1 to 8 carbon atoms, preferably from 1 to 6, morepreferably from 1 to 4 carbon atoms and from 0 to 3 heteroatoms;preferably from 0 to 2 heteroatoms; most preferably from 0 to 1heteroatoms. Where the systems contain heteroatoms, preferably theycontain 1 heteroatom. Preferred heteroatoms include O, S, and N; morepreferred are O, and N; and most preferred is O.

Preferably, R¹, R², R³, R⁵, and R⁶ are selected independently from anyof the systems defined for R⁴ above, and H.

In alternative embodiments, any of R¹, R², R³, R⁴, R⁵, and R⁶ groups aresubstituted. Preferably, the substituent(s) is selected from: (a) thegroup of C-linked monovalent substituents consisting of: (i) substitutedor unsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (ii) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (iii) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; said systemsof (i), (ii) and (iii) comprising from 1 to 10 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; (b) the group of S-linkedmonovalent substituents consisting of SA¹, SCN, SO₂A¹, SO₃A¹, SSA¹,SOA¹, SO₂NA¹A², SNA¹A², and SONA¹A²; (c) the group of O-linkedmonovalent substituents consisting of OA¹, OCN and ONA¹A²; (d) the groupof N-linked monovalent substituents consisting of NA¹A², (NA¹A²A³)⁺, NC,NA¹OA², NA¹SA², NCO, NCS, NO₂, N═NA¹, N═NOA¹, NA¹CN, NA¹NA²A³; (e) thegroup of monovalent substituents consisting of COOA¹, CON₃, CONA¹ ₂,CONA¹COA², C(═NA¹)NA¹A², CHO, CHS, CN, NC, and X; and (f) the groupconsisting fluoroalkyl monovalent substituents consisting of mono-,poly-, or per-fluoro alkyl systems comprising from 1 to 12 carbon atomsand 0 to 4 heteroatoms.

For the groups (b) to (e), described above, A¹, A², and A³ aremonovalent and are independently selected from: (1) H, (2) substitutedor unsubstituted, straight or branched, alkyl, mono- or poly-unsaturatedalkyl, heteroalkyl, aliphatic, heteroaliphatic, or heteroolefinicsystems, (3) substituted or unsubstituted, mono- or poly-cyclicaliphatic, aryl, or heterocyclic systems, or (4) substituted orunsubstituted, mono-, poly-, or per-fluoro alkyl systems; said systemsof (2), (3) and (4) comprising from 1 to 10 carbon atoms and 0 to 5heteroatoms selected from O, S, N, P, and Si; and wherein X is a halogenselected from the group consisting of F, Cl, Br, and I.

Preferred substituents for use herein include those having a HammettSigma Para (σ_(p)) Value from −0.65 to +0.75, preferably from −0.4 to+0.5. Hammett Sigma Values are described in Advanced OrganicChemistry—Reactions, Mechanisms and Structure (Jerry March, 5^(th) ed.(2001) at pages 368-375). Without being limited by theory, it isbelieved that substituents having sigma para values in the chosenranges, when substituted onto R¹ and/or R², may improve the compound'stoxicological profile without unduly adding an unfavourable increase inmolecular weight that may interfere with the molecule's ability topenetrate the hair shaft. Some preferred substituents and their HammettSigma Para values are shown below, in Table A. Additional substituentsand their values are shown in March, at page 370.

TABLE A Substituent NH₂ OH H COO— Cl COOH CF₃ σ_(p) −0.57 −0.38 0 0.110.24 0.44 0.53

Preferably the above defined radical scavengers have a pKa of more than7 to prevent the protonation of the nitrogen.

Alternative suitable radical scavengers for use herein are compoundsaccording to the general formula (II):

wherein R₁, R₂, R₃, R₄, and R₅ are each independently selected from H,COO⁻M⁺, Cl, Br, So₃ ⁻M⁺, NO₂, OCH₃, OH or a C¹ to C¹⁰ primary orsecondary alkyl and M is either H or alkali metal. Preferably, theabove-described radical scavengers have a pKa of more than 8.5 to ensureprotonation of the hydroxy group.

Other suitable radical scavengers for use herein include those selectedfrom group (III) benzylamine, imidazole, di-tert-butylhydroxytoluene,hydroquinone, guanine, pyrazine, piperidine, morpholine,methylmorpholine, 2 methyoxyethylamine, and mixtures thereof.

Preferred radical scavengers according to the present invention areselected from the classes of alkanolamines, amino sugars, amino acids,esters of amino acids and mixtures thereof. Particularly preferredcompounds are: monoethanolamine, 3-amino-1-propanol, 4-amino-1-butanol,5-amino-1-pentanol, 1-amino-2-propanol, 1-amino-2-butanol,1-amino-2-pentanol, 1-amino-3-pentanol, 1-amino-4-pentanol,3-amino-2-methylpropan-1-ol, 1-amino-2-methylpropan-2-ol,3-aminopropane-1,2-diol, glucosamine, N-acetylglucosamine, glycine,arginine, lysine, proline, glutamine, histidine, sarcosine, serine,glutamic acid, tryptophan, and mixtures thereof, and the salts such asthe potassium, sodium and ammonium salts thereof and mixtures thereof.

Especially preferred compounds are glycine, sarcosine, lysine, serine, 2methoxyethylamine, glucosamine, glutamic acid, morpholine, piperdine,ethylamine, 3 amino-1-propanol and mixtures thereof.

The radical scavengers according to the present invention preferablyhave a molecular weight of less than about 500, preferably less thanabout 300, more preferably less than about 250 in order to facilitatepenetration of the radical scavenger into the hair fibre. Thecompositions of the present invention preferably comprise from about0.1% to about 10% by weight, preferably from about 1% to about 7% byweight of radical scavenger. Preferably, the radical scavenger ispresent at an amount such that the weight ratio of radical scavenger tocarbonate ion is from 2:1 to 1:4. The radical scavenger is alsopreferably selected such that it is not an identical species as thealkalizing agent. According to one embodiment of the present inventionthe radical scavenger may be formed insitu in the hair dyeingcompositions prior to application to the hair fibres.

Thickeners

The composition of the present invention may optionally further compriseat least about 0.01% of thickeners. Thickeners are preferably comprisedin amount sufficient to provide the composition with a viscosity of fromabout 1 Pa·s to 40 Pa·s (1,000 to 40,000 cP) at 26° C. in order toprovide a composition that can be readily applied to the hair withoutdripping. Suitable thickeners for use herein may be chosen, for example,from:

-   -   (i) associative thickeners;    -   (ii) crosslinked acrylic acid homopolymers;    -   (iii) crosslinked copolymers of (meth)acrylic acid and of        (C1-C6)alkyl acrylate;    -   (iv) nonionic homopolymers and copolymers containing        ethylenically unsaturated monomers of ester and amide type;    -   (v) ammonium acrylate homopolymers and copolymers of ammonium        acrylate and of acrylamide;    -   (vi) polysaccharides; and    -   (vii) C12-C30 fatty alcohols.

-   (i) As used herein, the expression “associative thickener” means an    amphiphilic thickener comprising both hydrophilic units and    hydrophobic units, for example, at least one C8-C30 fatty chain and    at least one hydrophilic unit. Representative associative thickeners    that may be used are associative polymers chosen from:

-   (i) nonionic amphiphilic polymers comprising at least one fatty    chain and at least one hydrophilic unit;

-   (ii) anionic amphiphilic polymers comprising at least one    hydrophilic unit and at least one fatty-chain unit;

-   (iii) cationic amphiphilic polymers comprising at least one    hydrophilic unit and at least one fatty-chain unit; and

-   (iv) amphoteric amphiphilic polymers comprising at least one    hydrophilic unit and at least one fatty-chain unit;

The nonionic amphiphilic polymers comprising at least one fatty chainand at least one hydrophilic unit may, for example, be chosen from:

-   (1) celluloses modified with groups comprising at least one fatty    chain; for example: hydroxyethylcelluloses modified with groups    comprising at least one fatty chain chosen from alkyl, arylalkyl and    alkylaryl groups, and in which the alkyl groups are, for example,    C8-C22, such as the product Natrosol Plus Grade 330 CS(C16 alkyls)    sold by the company Aqualon, and the product Bermocoll EHM 100 sold    by the company Berol Nobel, and celluloses modified with    polyalkylene glycol alkylphenyl ether groups, such as the product    Amercell Polymer HM-1500 (polyethylene glycol (15) nonylphenyl    ether) sold by the company Amerchol.-   (2) hydroxypropyl guars modified with groups comprising at least one    fatty chain, such as the product Esaflor HM 22 (C22 alkyl chain)    sold by the company Lamberti, and the products Miracare XC95-3 (C14    alkyl chain) and RE205-1 (C20 alkyl chain) sold by the company    Rhodia Chimie.-   (3) polyether urethanes comprising at least one fatty chain, such as    C10-C30 alkyl or alkenyl groups, for instance the products Elfacos T    210 and Elfacos T 212 sold by the company Akzo or the products    Aculyn 44 and Aculyn 46 sold by the company Rohm & Haas.-   (4) copolymers of vinylpyrrolidone and of fatty-chain hydrophobic    monomers; examples that may be mentioned include: the products    Antaron V216 and Ganex V216 (vinylpyrrolidone/hexadecene copolymer)    sold by the company I.S.P., the products Antaron V220 and Ganex V220    (vinylpyrrolidone/eicosene copolymer) sold by the company I.S.P.-   (5) copolymers of C1-C6 alkyl acrylates or methacrylates and of    amphiphilic monomers comprising at least one fatty chain, such as    the oxyethylenated methyl methacrylate/stearyl acrylate copolymer    sold by the company Goldschmidt under the name Antil 208.-   (6) copolymers of hydrophilic acrylates or methacrylates and of    hydrophobic monomers comprising at least one fatty chain, such as    polyethylene glycol methacrylate/lauryl methacrylate copolymer.

The anionic amphiphilic polymers comprising at least one hydrophilicunit and at least one fatty-chain unit, may, for example, be chosen fromthose comprising at least one fatty-chain allyl ether unit and at leastone hydrophilic unit comprising an ethylenic unsaturated anionicmonomeric unit, for example, a vinylcarboxylic acid unit and further,for example, chosen from units derived from acrylic acids, methacrylicacids and mixtures thereof, wherein the fatty-chain allyl ether unitcorresponds to the monomer of formula below:CH2═C(R1)CH2OBnR   (I)in which R1 is chosen from H and CH3, B is an ethyleneoxy radical, n ischosen from zero and integers ranging from 1 to 100, R is chosen fromhydrocarbon-based radicals chosen from alkyl, arylalkyl, aryl, alkylaryland cycloalkyl radicals, comprising from 10 to 30 carbon atoms, and,further, for example, from 10 to 24 carbon atoms and even further, forexample, from 12 to 18 carbon atoms.

In one embodiment, a unit of formula (I) is, for example, a unit inwhich R1 can be H, n can be equal to 10 and R can be a stearyl (C18)radical.

Anionic amphiphilic polymers of this type are described and prepared,according to an emulsion polymerization process, in patent EP-0 216 479B2.

In one embodiment, anionic amphiphilic polymers are, for example,polymers formed from 20% to 60% by weight of acrylic acid and/or ofmethacrylic acid, from 5% to 60% by weight of lower alkyl(meth)acrylates, from 2% to 50% by weight of fatty-chain allyl ether offormula (I), and from 0% to 1% by weight of a crosslinking agent whichis a well-known copolymerizable unsaturated polyethylenic monomer, forexample, diallyl phthalate, allyl (meth)acrylate, divinylbenzene,(poly)ethylene glycol dimethacrylate and methylenebisacrylamide.

Examples of such polymers are crosslinked terpolymers of methacrylicacid, of ethyl acrylate and of polyethylene glycol (10 EO) stearyl ether(Steareth-10), such as those sold by the company Ciba under the namesSalcare SC 80 and Salcare SC 90, which are aqueous 30% emulsions of acrosslinked terpolymer of methacrylic acid, of ethyl acrylate and ofsteareth-10 allyl ether (40/50/10).

The anionic amphiphilic polymers may further be chosen, for example,from those comprising at least one hydrophilic unit of unsaturatedolefinic carboxylic acid type, and at least one hydrophobic unit of thetype such as a (C10-C30) alkyl ester of an unsaturated carboxylic acid.The hydrophilic unit of unsaturated olefinic carboxylic acid typecorresponds to, for example, the monomer of formula (II) below:

in which R1 is chosen from H, CH3, and C2H5, i.e. acrylic acid,methacrylic acid and ethacrylic acid units. And the hydrophobic unit ofthe type such as a (C10-C30) alkyl ester of an unsaturated carboxylicacid corresponds to, for example, the monomer of formula (III) below:

in which R1 is chosen from H, CH3, and C2H5 (i.e. acrylate, methacrylateand ethacrylate units) and is, for example, chosen from, for example, H(acrylate units) and CH3 (methacrylate units), R2 is chosen from C10-C30alkyl radicals, for example, C12-C22 alkyl radical.

Examples of (C10-C30)alkyl esters of unsaturated carboxylic acidsinclude lauryl acrylate, stearyl acrylate, decyl acrylate, isodecylacrylate, and dodecyl acrylate, and the corresponding methacrylates,lauryl methacrylate, stearyl methacrylate, decyl methacrylate, isodecylmethacrylate and dodecyl methacrylate.

Anionic amphiphilic polymers of this type are disclosed and prepared,for example, according to U.S. Pat. No. 3,915,921 and U.S. Pat. No.4,509,949.

Representative anionic amphiphilic polymers that can be used may furtherbe chosen from polymers formed from a mixture of monomers comprising:

-   (i) acrylic acid, an ester of formula (IV) below:

in which R1 is chosen from H and CH3, R2 is chosen from C10-C30 alkylradicals, such as alkyl radicals comprising from 12 to 22 carbon atoms,and a crosslinking agent; such as polymers derived from 95% to 60% byweight of the acrylic acid (hydrophilic unit), 4% to 40% by weight ofC10-C30 alkyl acrylate (hydrophobic unit), and 0% to 6% by weight ofcrosslinking polymerizable monomer, or polymers derived from 98% to 96%by weight of the acrylic acid (hydrophilic unit), 1% to 4% by weight ofC10-C30 alkyl acrylate (hydrophobic unit) and 0.1% to 0.6% by weight ofcrosslinking polymerizable monomer; or

-   (ii) acrylic acid and lauryl methacrylate, such as the polymers    formed from 66% by weight of acrylic acid and 34% by weight of    lauryl methacrylate.

The crosslinking agent can be a monomer comprising a group (V)

with at least one other polymerizable group whose unsaturated bonds arenot conjugated with respect to one another. Mention may be made, forexample, of polyallyl ethers such as polyallylsucrose and polyallylpentaerythritol.

Among said polymers above mention may be made, for example, of theproducts sold by the company Noveon under the trade names Pemulen TR1,Pemulen TR2, Carbopol 1382, and further, for example, Pemulen TR1, andthe product sold by the company S.E.P.C. under the name Coatex S X.

Suitable anionic amphiphilic fatty-chain polymers, include for examplethe methacrylic acid/methyl acrylate/ethoxylated alkyldimethyl-meta-isopropenylbenzylisocyanate copolymer sold under the nameViscophobe DB 1000 by the company Amerchol.

The cationic amphiphilic polymers used are, for example, chosen fromquaternized cellulose derivatives and polyacrylates comprising aminoside groups.

The quaternized cellulose derivatives are, for example, chosen from;quaternized celluloses modified with groups comprising at least onefatty chain, such as alkyl, arylalkyl and alkylaryl groups comprising atleast 8 carbon atoms, and mixtures thereof, quaternizedhydroxyethylcelluloses modified with groups comprising at least onefatty chain, such as alkyl, arylalkyl and alkylaryl groups comprising atleast 8 carbon atoms, and mixtures thereof.

Quaternized and non-quaternized polyacrylates comprising amino sidegroups having for example, hydrophobic groups, such as Steareth 20(polyoxy-ethylenated(20) stearyl alcohol) and (C10-C30)alkyl PEG-20itaconate.

The alkyl radicals borne by the above quaternized celluloses andhydroxyethylcelluloses, for example, contain from 8 to 30 carbon atoms.The aryl radicals, for example, are chosen from phenyl, benzyl, naphthyland anthryl groups.

Examples of quaternized alkylhydroxyethyl-celluloses comprising C8-C30fatty chains are the products Quatrisoft LM 200, Quatrisoft LM-X529-18-A, Quatrisoft LM-X 529-18B (C12 alkyl) and Quatrisoft LM-X 529-8(C18 alkyl) sold by the company Amerchol, and the products Crodacel QM,Crodacel QL (C12 alkyl) and Crodacel QS (C18 alkyl) sold by the companyCroda.

Examples of polyacrylates comprising amino side chains is Structure Plusfrom the company National Starch.

Among amphoteric amphiphilic polymers comprising at least onehydrophilic unit and at least one fatty-chain unit, mention may be made,for example, of methacrylamidopropyltrimethylammonium chloride/acrylicacid/C10-C30 alkyl methacrylate copolymers, wherein the alkyl radicalis, for example, a stearyl radical.

-   (ii) Among the crosslinked acrylic acid homopolymers that may be    mentioned are those crosslinked with an allylic alcohol ether of the    sugar series, such as the products sold under the names Carbopol    980, 981, 954, 2984 and 5984 by the company Noveon or the products    sold under the names Synthalen M, Synthalen L and Synthalen K by the    company 3V Sigma.-   (iii) Crosslinked copolymers of (meth)acrylic acid and of C1-C6    alkyl acrylate can be chosen from crosslinked copolymers of    methacrylic acid and of ethyl acrylate as an aqueous dispersion    comprising 38% active material sold, for example, under the name    Viscoatex 538C by the company Coatex, and crosslinked copolymers of    acrylic acid: and of ethyl acrylate as an aqueous dispersion    comprising 28% active material sold under the name Aculyn 33 by the    company Rohm & Haas. Crosslinked copolymers of methacrylic acid and    of ethyl acrylate include an aqueous dispersion comprising 30%    active material manufactured and sold under the name Carbopol Aqua    SF-1 by the company Noveon.-   (iv) Among the nonionic homopolymers or copolymers comprising    ethylenically unsaturated monomers of ester and/or amide type,    mention may be made of the products sold under the names: Cyanamer    P250 by the company Cytec (polyacrylamide); PMMA MBX-8C by the    company US Cosmetics (methyl methacrylate/ethylene glycol    dimethacrylate copolymer); Acryloid B66 by the company Rohm & Haas    (butyl methacrylate/methyl methacrylate copolymer); BPA 500 by the    company Kobo (polymethyl methacrylate).-   (v) Ammonium acrylate homopolymers that may be mentioned include the    product sold under the name Microsap PAS 5193 by the company    Hoechst.

Copolymers of ammonium acrylate and of acrylamide include the productsold under the name Bozepol C Nouveau or the product PAS 5193 sold bythe company Hoechst (which are described and prepared in documents FR-2416 723, U.S. Pat. No. 2,798,053 and U.S. Pat. No. 2,923,692).

-   (vi) The polysaccharides are, for example, chosen from glucans,    modified and unmodified starches (such as those derived, for    example, from cereals, for instance wheat, corn or rice, from    vegetables, for instance yellow pea, and tubers, for instance potato    or cassaya), amylose, amylopectin, glycogen, dextrans, celluloses    and derivatives thereof (methylcelluloses, hydroxyalkylcelluloses,    ethyl hydroxyethylcelluloses, and carboxymethylcelluloses), mannans,    xylans, lignins, arabans, galactans, galacturonans, chitin,    chitosans, glucuronoxylans, arabinoxylans, xyloglucans,    glucomannans, pectic acids and pectins, alginic acid and alginates,    arabinogalactans, carrageenans, agars, glycosaminoglucans,    succinoglucans, gum arabics, gum tragacanths, ghatti gums, karaya    gums, carob gums, galactomannans, such as guar gums, and nonionic    derivatives thereof (hydroxypropyl guar) and xanthan gums, and    mixtures thereof.

For example, suitable polysaccharides are described in “Encyclopedia ofChemical Technology”, Kirk-Othmer, Third Edition, 1982, volume 3, pp.896-900, and volume 15, pp. 439-458, in “Polymers in Nature” by E. A.MacGregor and C. T. Greenwood, published by John Wiley & Sons, Chapter6, pp. 240-328, 1980, and in “Industrial Gums-Polysaccharides and theirDerivatives”, edited by Roy L. Whistler, Second Edition, published byAcademic Press Inc., the content of these three publications beingentirely incorporated by reference.

For example, starches, guar gums and celluloses and derivatives thereofcan be used. Suitable starches include for example, of macromolecules inthe form of polymers comprising elemental moieties that areanhydroglucose units. The number of these moieties and their assemblymake it possible to distinguish between amylose (linear polymer) andamylopectin (branched polymer). The relative proportions of amylose andof amylopectin, and also their degree of polymerization, can vary as afunction of the botanical origin of the starches. The botanical originof the starch molecules used may be cereals or tubers. Thus, thestarches can be, for example, chosen from corn starch, rice starch,cassaya starch, tapioca starch, barley starch, potato starch, wheatstarch, sorghum starch and pea starch. Starches are generally in theform of a white powder, which is insoluble in cold water and which hasan elementary particle size ranging from 3 to 100 microns. The starchesmay optionally be C1-C6 hydroxyalkylated or C1-C6 acylated (such asacetylated). The starches may also have undergone heat treatments.Distarch phosphates or of compounds rich in distarch phosphate, forinstance the products sold under the references Prejel VA-70-T AGGL(gelatinized hydroxypropylated cassaya distarch phosphate) or Prejel TK1(gelatinized cassaya distarch phosphate) or Prejel 200 (gelatinizedacetylated cassaya distarch phosphate) by the company Avebe, orStructure ZEA from National Starch (hydroxypropylated corn distarchphosphate), Structure XL from National Starch (hydroxypropylated starchphosphate) may also be used.

The guar gums may be modified or unmodified. The unmodified guar gumsare, for example, the products sold under the name Vidogum GH 175 by thecompany Unipectine and under the names Meyro-Guar 50 and Jaguar C by thecompany Meyhall. The modified nonionic guar gums are, for example,modified with C1-C6 hydroxyalkyl groups. Among hydroxyalkyl groups,mention may be made, for example, of hydroxymethyl, hydroxyethyl,hydroxypropyl and hydroxybutyl groups. These guar gums are well known inthe state of the art and can be prepared, for example, by reactingcorresponding alkene oxides, such aspropylene oxides, with guar gum soas to obtain a guar gum modified with hydroxypropyl groups. The degreeof hydroxyalkylation, which corresponds to the number of alkylene oxidemolecules consumed by the number of free hydroxyl functions present onthe guar gum, may, for example, range from 0.4 to 1.2.

Such nonionic guar gums optionally modified with hydroxyalkyl groups aresold, for example, under the trade names Jaguar HP8, Jaguar HP60 andJaguar HP120, Jaguar DC 293 and Jaguar HP 105 by the company RhodiaChimie (Meyhall) or under the name Galactasol 4H4FD2 by the companyAqualon.

Suitable celluloses include for example, hydroxyethylcellulose andhydroxypropylcelluloses, such as the products sold under the namesKlucel EF, Klucel H, Klucel LHF, Klucel MF and Klucel G by the companyAqualon.

-   (vii) The C12- C30 fatty alcohols are, for example, chosen from    myristyl alcohol, cetyl alcohol, stearyl alcohol, behenyl alcohol or    mixture thereof. When fatty alcohols are used as thickeners, at    least one additional surfactant with HLB value above about 6 is    commonly included to form bi-layers with fatty alcohols. The most    useful bi-layer structures include gel network phase where parallel    bi-layers of fatty alcohols are swollen by water forming semi-solid    creams, and vesicle dispersions where fatty alcohols bi-layers are    curved into approximately spherical uni-lamellar or multi-lamellar    aggregates.

Preferred for use herein are salt tolerant thickeners. A non exclusivelist of suitable salt tolerant thickeners for use herein includexanthan, guar, hydroxypropyl guar, scleroglucan, methyl cellulose, ethylcellulose (commercially available as Aquacote®), hydroxyethyl cellulose(Natrosol®), carboxymethyl cellulose, hydroxypropylmethyl cellulose,microcrystalline cellulose, hydroxybutylmethyl cellulose, hydroxypropylcellulose (Klucel®), hydroxyethyl ethyl cellulose, cetyl hydroxyethylcellulose (Natrosol® Plus 330), N-vinylpyrollidone (Povidone®),Acrylates/Ceteth-20 Itaconate Copolymer (Structure® 3001), hydroxypropylstarch phosphate (Structure® ZEA), polyethoxylated urethanes orpolycarbamyl polyglycol ester (e.g. PEG-150/Decyl/SMDI copolymer=Aculyn®44, PEG-150/Stearyl/SMDI copolymer=Aculyn 46®), trihydroxystearin(Thixcin®) acrylates copolymer (e.g. Aculyn® 33) or hydrophobicallymodified acrylate copolymers (e.g. Acrylates/Steareth-20 MethacrylateCopolymer=Aculyn® 22), and Crodafos CES®.

Conditioning Agent

The compositions of the present invention may comprise or are used incombination with a composition comprising a conditioning agent.Conditioning agents suitable for use herein are selected from siliconematerials, amino silicones, fatty alcohols, polymeric resins, polyolcarboxylic acid esters, cationic polymers, cationic surfactants,insoluble oils and oil derived materials and mixtures thereof.Additional materials include mineral oils and other oils such asglycerin and sorbitol.

The conditioning agent will generally be used at levels of from about0.05% to about 20% by weight of the composition, preferably of fromabout 0.1% to about 15%, more preferably of from about 0.2% to about10%, even more preferably of from about 0.2% to about 2%.

Particularly useful conditioning materials are cationic polymers.Conditioners of cationic polymer type may be chosen from those alreadyknow by those skilled in the art as improving at least one cosmeticproperties of keratin fibres treated with a cosmetic composition.Cationic polymers can be chosen from those comprising units of at leastone amine group chosen from primary, secondary, tertiary and quaternaryamine groups that may either form part of the main polymer chain, or beborne by a side substituant that is directly attached to the mainpolymer chain. Such cationic polymers generally have a number averagemolecular mass ranging from 500 to 5×10⁶, or more preferably from 1000to 3×10⁶. Polymers of the polyamine, polyamino amide and polyquaternaryammonium type that may be used include but are not limited to:

-   1) Homopolymers and copolymers derived from acrylic or methacrylic    esters or amides. Copolymers of these polymers can also comprise at    least one unit derived from comonomers which may be chosen from the    family of acrylamides, methacrylamides, diacetone acylamides,    acrylamides and methacrylicamides substituted on the nitrogen with    at least one group chosen from lower (C1-C4) alkyls, acrylic and    methacrylic acids and esters thereof, vinlylactams such as    vinlypyrrolidone and vinylcaprolactam, and vinyl esters. Examples of    such polymers include:

Copolymers of acrylamide and of methacryloyloxyethyltrimethylammoniummethosulfate, examples of which include polymers known via the INCInomenclature as Polquaternium-5, such as the products sold under thenames Reten 210, Reten 220, Reten 230, Reten 240, Reten 1104, Reten1105, Reten 1006 by the company Hercules and Merquat 5, Merquat 5 SF bythe company Nalco.

Copolymers of vinylpyrrolidone and dimethylaminopropyl methacrylamide,examples of which include polymers known via the INCI nomenclature asPolyquaternium-28, such as the products sold under the name GafquatHS-100 by the company International Speciality Products (ISP).

Coplolymers of vinyl pyrrolidone and dialkyaminoalkyl acrylates ormethactylates, examples of which include polymers known via the INCInomenclature as Polquatemium-11, such as the products sold under thename Gafquat 440, Gafquat 734, Gafquat 755, Gafquat 755N by the companyInternational Speciality Products (ISP), and Luviquat PQ11 PM by thecompany BASF and Polyquat-11 SL by the company Sino Lion.

Copolymers vinylpyrrolidone, dimethylaminopropyl methacrylamide andmethacryloylaminopropyl lauryldimonium chloride, examples of whichinclude polymers known via the INCI nomenclature as polyquaternium-55,such as the products sold under the name Styleze W-20 by the companyInternational Speciality Products (ISP).

Copolymers of acrylic acid, acrylamide and methacrylamidopropyltrimoniumchloride, examples of which include polymers known via the INCInomenclature as Polyquaternium-53, such as the products sold under thename Merquat 2003 by the company Nalco.

Copolymers of dimethyaminopropylacrylate (DMAPA), acrylic acid andacrylonitrogens and diethyl sulfate, examples of which include polymersknown via the INCI nomenclature as Polyquaternium-31, such as theproducts sold under the name Hypan QT100 by the company Lipo.

Copolymers of acrylamide, acrylamidopropyltrimonium chloride,2-amidopropylacrylamide sulfonate, and dimethyaminopropylacrylate(DMAPA), examples of which include polymers known via the INCInomenclature as polyquaternium-43, such as the products sold under thename Bozequat 4000 by the company Clairant.

Copolymers of acrylic acid, methylacrylate andmethacrylamidopropyltrimonium chloride, examples of which includepolymers known via the INCI nomenclature as Polyquatemium-47, such asthe products sold under the name Merquat 2001 and Merquat 2001N soldcommercially by Nalco.

Copolymes of methacryloyl ethyl betaine, 2-hydroxyethyl methacrylate andmethacryloyl ethyl trimethyl ammonium chloride, examples of whichinclude polymers known via the INCI nomenclature as Polyquaternium-48,such as the products sold under the name Plascize L-450 by the companyGoo Chemcial.

Copolymers of acrylic acid diallyl dimethyl ammonium chloride andacrylamide, examples of which include polymers known via the INCInomenclature as polyquaternium 39, such as the products sold under thename Merquat 3330 and Merquat 3331 by the company Nalco.

Further examples include copolymers of methacrylamidemethacrylamido-propyltrimonium and methacryloylethyltrimethyl ammoniumchloride and their derivatives, either homo or copolymerised with othermonomers, examples of which include polymers known via the INCInomenclature as: Polyquaternium-8, Polyquaternium-9, Polyquaternium-12,Polyquaternium-13 Polyquaternium-14, Polyquaternium-15, such as theproducts sold under the name Rohagit KF 720 F by the company Rohm,Polyquaternium-30, such as the products sold under the name Mexomere PXby the company Chimex, Polyquaternium-33, Polyquaternium-35,Polyquaternium-36, such as the products sold under the name Plex 3074 Lby the company Rhon, Polyquaternium 45, such as the products sold underthe name Plex 3073L by the company Rohn, Polyquatemium 49, such as theproducts sold under the name Plascize L-440 by the company GooChemicals, Polyquaternium 50 such as the products sold under the namePlascize L-441 by the company Goo Chemicals, Polyquaternium-52.

-   2) Cationic polysaccharides, such as cationic celluloses and    cationic galactomannan gums. Among the cationic polysaccharides that    maybe mentioned, for example, are cellulose ether derivatives    comprising quaternary ammonium groups and cationic cellulose    copolymers or cellulose derivatives grafted with a water-soluble    quaternary ammonium monomer and cationic galactomannan gums.    Examples include but are not limited to

Copolymers of hydroxyethylcelluloses and diallyldimethyl ammoniumchlorides, examples of which include polymers known via the INCInomenclature as Polyquaternium-4, such as the products sold under thename Celquat L 200 and Celquat H 100 by the company National Starch.

Copolymers of hydroxyethylcelluloses and a trimethyl ammoniumsubstituted epoxide, examples of which include polymers known via theINCI nomenclature as Polyquaternium-10, such as the products sold underthe name AEC Polyquatemium-10 by the company A&E Connock, Catinal C-100Catinal HC-35 Catinal HC-100 Catinal HC-200 Catinal LC-100 CatinalLC-200 by the company Toho, Celquat SC-240C Celquat SC-230M, by thecompany National Starch, Dekaquat 400, Dekaquat 3000 by the companyDekker, Leogard GP by the company Akzo Nobel, RITA Polyquta 400 RITA,Polyquta 3000 by the company RITA, UCARE Polymer JR-125 UCARE PolymerJR-400 UCARE Polymer JR-30M UCARE Polymer LK UCARE Polymer LR 400 UCAREPolymer LR 30M by the company Amerchol.

Copolymers of hydroxyethylcelluloses and lauryl dimethyl ammoniumsubstituted epoxides, examples of which include polymers known via theINCI nomenclature as Polyquaternium-24, such as the products sold underthe name Quatrisoft polymer LM-200 by the company Amerchol.

Derivatives of Hydroxypropyl Guar, examples of which include polymersknown via the INCI nomenclature as Guar Hydroxypropyltrimonium Chloride,such as the products sold under the name Catinal CG-100, Catinal CG-200by the company Toho, Cosmedia Guar C-261N, Cosmedia Guar C-261N,Cosmedia Guar C-261N by the company Cognis, DiaGum P 5070 by the companyFreedom Chemical Diamalt, N-Hance Cationic Guar by the companyHercules/Aqualon, Hi-Care 1000, Jaguar C-17, Jaguar C-2000, JaguarC-13S, Jaguar C-14S, Jaguar Excel by the company Rhodia, Kiprogum CW,Kiprogum NGK by the company Nippon Starch.

Hydroxypropyl derivatives of Guar Hydroxypropyltrimonium Chloride,examples of which include polymers known via the INCI nomenclature asHydroxypropyl Guar Hydroxypropyltrimonium Chloride, such as the productssold under the name Jagaur C-162 by the company Rhodia.

-   3) Polyamino amide derivatives resulting from the condensation of    polyalkylene polyamines with polycarboxylic acids followed by    alkylation with difunctional agents. Among the derivative, mention    may be made for example to adipic    acid/dimethylaminohydroxypropyl/diethylenetriamine.-   4) Polymers obtained by reaction of a polyalkylene polyamine    comprising two primary amines groups and at last one secondary amine    group with a decarboxylic acid chosen from diglycolic acids and    saturated aliphatic dicarboxylic acids comprising from 3 to 8 carbon    atoms. Non-limiting examples of such derivatives include the adipic    acid/epxoypropyl/diethylenetriamine.-   5) Cyclopolymers of dialkdiallylamine or of dialkyldiallyammonium,    among which polymers mention may be made of:

Dimethyldiallyammonium chloride polymers, examples of which includepolymers known via the INCI nomenclature as Polyquatemium-6, such as theproducts sold under the name Merquat 100 by the company Nalco, Mirapol100 by the company Rhodia, Rheocare CC6 by the company CosmeticRheologies, AEC polyquaternium-6 by the company A&E Connock, Agequat 400by the company CPS, Conditioner P6 by the company 3V Inc., Flocare C106by the company SNF, Genamin PDAC by the company Clariant, Mackernium 006by the company McIntyre.

Copolymers of acrylamides and dimethyldiallylammonium chloridesmonomers, examples of which include polymers known via the INCInomenclature as Polyquaternium-7, such as the products sold under thename AEC Polyquaternium-7 by the company A&E Connock, Agequat-5008,Agequat C-505 by the company CPS, Conditioner P7 by the company 3V Inc.Flocare C 107 by the company SNF Mackemium 007, Mackernium 007S by thecompany McIntyre, ME Polymer 09W by the company Toho, Merquat 550,Merquat 2200, Merquat S by the company Nalco, Mirapol 550 by the companyRhodia, Rheocare CC7, Rheocare CCP7 by the company Cosmetic Rheologies,Salcare HSP-7, Salcare SC10, Salcare Super 7 by the company Ciba.

Copolymers of dimethyldiallylammoniumchlorides and acrylic acids,examples of which include polymers known via the INCI nomenclature aspolyquatemary-22, such as the products sold under the name Merquat 280and Merquat 295 by the company Nalco.

-   6) Quaternary diammonium polymers comprising repeat units    corresponding to [—N+(R1)(R2)-A1-N+(R3)(R4)-B1-][2X—], in which R1,    R2, R3 and R4, which may be identical or different, are chosen from    aliphatic, alicyclic and arylaliphatic radicals comprising from 1 to    20 carbon atoms and from lower hydroxyalkylaliphatic radicals, or    R1, R2, R3 and R4, together or separately, constitute, with the    nitrogen atoms to which they are attached, heterocycles optionally    comprising a second heteroatom other then nitrogen, or R1, R2, R3    and R4, are choen from liner or branched C1-C6 alkyl radicals    substituted with at least one group chosen from nitrile, ester, acyl    and amide groups and groups of —CO—O—R5-D and —CO—NH—R5-D wherein R5    is chosen from alkylene groups and D is chosen from quaternary    ammonium groups. A1 and B1, which may be identical or different, are    chosen from linear and branched, saturated or unsaturated    polymethylene groups comprising 2 to 20 carbon atoms. The    polymethylene groups may comprise, linked to or intercalated in the    main ring, at least one entity chosen from aromatic rings, oxygen    and sulphur atoms and sulphoxide, sulphone, disulphide, amino,    alkylamino, hydroxyl, quaternary, ammonium, ureido, amide and ester    groups, and X— is an anion derived from inorganic and organic acids.    D is chosen from a glycol residue, a bis-secondary diamine residue,    a bis-primary diamine residue or a ureylene group. An examples of    which include polymers known via the INCI nomenclature as    Hexadimethrine chloride, where R1, R2, R3 and R4 are each methyl    radicals, A1 is (CH2)3 and B1 is (CH2)6 and X═Cl. Further examples    of which include polymers known via the INCI nomenclature as    polyquatemium-34 where R1 and R2 are ethyl radicals and R3 and R4    are methyl radicals and A1 is (CH2)3 and B1 is (CH2)3 and X═Br, such    as the products sold under the name Mexomere PAX by the company    Chimax.-   7) Polyquaternary ammonium polymers comprising repeating units of    formula    [—N+(R6)(R7)-(CH2)r—NH—CO—(CH2)q—CO)t—NH—(CH2)s—N+(R8)(R9)-A-][2X—],    in which R6, R7, R8 and R9 which may be identical or different, are    chosen from a hydrogen atom and a methyl, ethyl, propyl,    α-hydroxyethyl, α-hydroxypropyl, and —CH2CH2(OCH2CH2)pOH radicals,    wherein p is equal to 0 or an integer ranging from 1 to 6, wherein    R6, R7, R8 and R9 do not all simultaneously represent a hydrogen    atom. R and s which maybe identical or different are each an integer    ranging from 1 to 6, q is equal to 0 or an integer ranging from 1 to    34 and X— is anion such as a halide. T is an integer chosen to be    equal to 0 or 1. A is chosen from divalent radicals such as    —CH2-CH2-O—CH2-CH2-. Examples of which include

Polymers known via the INCI nomenclature as polyquatemium-2, wherer=s=3, q=0,t=0, R6, R7, R8 and R9 are methyl groups, and A is—CH2-CH2-O—CH2-CH2, such as the products sold under the name Ethpol PQ-2from Ethox and Mirapol A-15 by the company Rhodia.

Polymers known via the INCI nomenclature as polyquaternium-17 wherer=s=3, q=4, t=1 R6, R7, R8 and R9 are methyl groups, and A is—CH2-CH2-O—CH2-CH2.

Polymers known via the INCI nomenclature as Polyquatemium 18, wherer=s=3, q=7, t=1 R6, R7, R8 and R9 are methyl groups, and A is—CH2-CH2-O—CH2-CH2

Polymers known via the INCI nomenclature as the block copolymer formedby the reaction of Polyquaternium-2 with Polyquaternium-17, known asPolyquaternium 27, such as the products sold under the name Mirapol 175by the company Rhodia.

-   8) Copolymers of vinylpyrrolidones and of vinylimidazoles and    optionally vinylcaprolactums, examples of which include polymers    known via the INCI nomenclature as Polyquaternary-16 formed from    methylvinylimidazolium chlorides and vinylpyrrolidones, such as the    products sold under the name Luviquat FC370, Luviquat FC550,    Luviquat FC905, Luviquat HM-552 by the company BASF. Or copolymers    of vinylcaprolactams and vinylpyrrolidones with    rnethylvinylimidazolium methosulfates, examples of which include    polymers known via the INCI nomenclature as Polyquaternium-46, such    as the products sold under the name Luviquat Hold by the company    BASF. Or copolymers of vinylpyrrolidones and quaternized    imidazolines, examples of which include polymers known via the INCI    nomenclature poylquaterary 44, such as the products sold under the    name Luviquat Care by the company BASF-   9) Polyamines such as the product Polyquart H sold by Cognis under    the reference name polyethylene glycol (15) tallow polyamine in the    CTFA dictionary.-   10) Cross linked methacryloyloxy(C1-C4)alkyltri(C1-C4)alkylammonium    salt polymers such as the polymers obtained by homopolymerisation of    dimethylaminoethyl methacrylates quaternized with methyl chloride,    or by copolymerisation of acrylamides with dimethylaminoethyl    methacrylates quaternized with methyl chloride, the homo or    copolymerisation being followed by crosslinking with a compound    comprising olefinic unsaturation, such as methylenebisacrylamides,    examples of which include polymers known via the INCI nomenclature    as Polyquaternium-37, such as the products sold under the name    Synthalen, C N Synthalen C R, Synthalen C U, sold by 3V sigma, or as    a dispersion in another media such as the products sold under the    name Salcare SC95 and Salcare SC96 by the company Ciba or Rheocare    CTH(E) by the company Cosmetic Rheologies. Or in another example of    which include polymers known via the INCI nomenclature as    Polyquatemium-32, or when sold as a dispersion in mineral oil such    as the products sold under the name Salcare SC92 by the company    Ciba.-   11) Further examples of cationic polymers include polymers known via    the INCI nomenclature as Polyquatemium 51, such as the products sold    under the name Lipidure-PMB by the company NOF, via the INCI    nomenclature as Polyquaternium 54, such as the products sold under    the name Qualty-Hy by the company Mitsui, and via the INCI    nomenclature as Polyquaternium 56 such as the products sold under    the name Hairrol UC-4 by the company Sanyo chemicals.-   12) Silicone polymers comprising cationic groups and/or groups which    may be ionised into cationic groups. For example: cationic silicones    of the general formula    (R10-N+(CH3)2)-R11(Si(CH3)2-O)x-R11-(N+(CH3)2)-R10), where R10 is an    alkyl derived from coconut oil, and R11 is (CH2CHOCH2O(CH2)3 and x    is a number between 20 and 2000, examples of which include polymers    known by the INCI nomenclature as Quaternium 80, such as the    products sold under the name as Abil Quat 3272 and Abil Quat 3474    sold commercially by Goldschmidt.

Silicones containing groups which may be ionised into cationic groups,for example aminosilicones containing at least 10 repeating siloxane—(Si(CH3)2-O) units within the polymer chain, with either terminal,graft or a mixture of terminal and graft aminofunctional groups. Examplefunctional groups are not limited to aminoethylaminopropyl,aminoethylaminoisobutly, aminopropyl. In the case of graft polymers, theterminal siloxane units can either be (CH3)3Si—O or R12(CH3)2Si—O, whereR12 can be either OH or OR13, where R13 is a C1-C8 alky group, or amixture of both functional terminal groups. These silicones are alsoavailable as preformed emulsions. Polymer with terminal siloxane unitsof (CH3)3Si—O examples of which include polymers known by the INCInomenclature as trimethylsilylamodimethicone, such as the products soldunder the name as DC-2-8566, DC 7224 and DC-2-8220 sold commercially byDow Coming and SF1708 and SM 2125 sold commercially by GE Silicones andWacker Belsil ADM 653 sold commercially by Wacker silicones. Furtherexamples include polymers with terminal siloxane units of(R12O)(CH3)2Si—O where R12 can be either OH or OR13, where R13 is aC1-C8 alky group, or a mixture of both functional terminal groups, knownby the INCI nomenclature as amodimethicone, such as the products soldunder the name as Wacker Belsil ADM 1100, Wacker Belsil ADM 1600, WackerBelsil ADM 652, Wacker Belsil ADM 6057E, Wacker Belsil ADM 8020 soldcommercial by Wacker Silicones, DC929, DC939, DC949 and DC AP6087 soldcommercially by Dow Corning and SM2059 sold commercially by GEsilicones.

Silicones containing groups which may be ionised into cationicgroups—for example silicones containing at least 10 repeating siloxane—(Si(CH3)2-O) units within the polymer chain, with either terminal,graft or a mixture of terminal and graft aminofunctional groups,together with additional functional groups. Additional functional groupscan include polyoxyalkylene, the reaction product of amines andcarbinols, alky chains. For example products know by the INCInomenclature as methoxy PEG/PPG-7/3 Aminopropyl Dimethicone, such as theproduct sold under the name of Abil Soft AF100 sold commercially byDegussa. For example products know by the INCI nomenclature as Bis(C13-15 Alkoxy) PG Amodimethicone, such as the product sold under thename of DC 8500 sold commercially by Dow Corning.

Surfactants

The compositions according to the present invention may further compriseone or more surfactants. Surfactants suitable for use herein generallyhave a lipophilic chain length of from about 8 to about 30 carbon atomsand can be selected from anionic, nonionic, amphoteric and cationicsurfactants and mixtures thereof. The total level of surfactant is fromabout 1% to about 60%, preferably from about 2% to about 30%, morepreferably from about 8% to about 25% and especially from about 10% toabout 20% by weight.

The compositions of the invention preferably comprise a mixture ofanionic and amphoteric surfactants with one or more nonionicsurfactants. Anionic components, where may be present in the range offrom about 0.1% to about 20%, preferably from about 0.1% to about 15%,and more preferably from about 5% to about 15% by weight of thecomposition; amphoteric or nonionic components, may independently bepresent is in the range from about 0.1% to about 15% by weight,preferably from about 0.5% to about 10%, more preferably from about 1%to about 8% by weight.

As examples of anionic surfactants, which can be used, alone or asmixtures, mention may be made, for example, of salts (such as alkalinesalts, for example, sodium salts, ammonium salts, amine salts, aminoalcohol salts and magnesium salts) of the following compounds: alkylsulphates, alkyl ether sulphates, alkylamido ether sulphates,alkylarylpolyether sulphates, monoglyceride sulphates; alkylsulphonates, alkyl phosphates, alkylamide sulphonates, alkylarylsulphonates, a-olefin sulphonates, paraffin sulphonates; alkylsulphosuccinates, alkyl ether sulphosuccinates, alkylamidesulphosuccinates; alkyl sulphosuccinamates; alkyl sulphoacetates; alkylether phosphates; acyl sarcosinates; acyl isethionates andN-acyltaurates. The alkyl or acyl radical of all of these variouscompounds, for example, comprises from 8 to 24 carbon atoms, and thearyl radical, for example, is chosen from phenyl and benzyl groups.Among the anionic surfactants, which can also be used, mention may alsobe made of fatty acid salts such as the salts of oleic, ricinoleic,palmitic and stearic acids, coconut oil acid or hydrogenated coconut oilacid; acyl lactylates in which the acyl radical comprises from 8 to 20carbon atoms. Weakly anionic surfactants can also be used, such asalkyl-D-galactosiduronic acids and their salts, as well aspolyoxyalkylenated (C₆-C₂₄) alkyl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylaryl ether carboxylic acids,polyoxyalkylenated (C₆-C₂₄) alkylamido ether carboxylic acids and theirsalts, for example, those comprising from 2 to 50 ethylene oxide groups,and mixtures thereof. Anionic derivatives of polysaccharides, forexample carboxyalkyl ether of alkyl polyglucosides, can be also used.

The nonionic surfactants are compounds that are well known (see, forexample, in this respect “Handbook of Surfactants” by M. R. Porter,published by Blackie & Son (Glasgow and London), 1991, pp. 116-178).They can be chosen, for example, from polyethoxylated, polypropoxylatedand polyglycerolated fatty acids, alkyl phenols, α-diols and alcoholscomprising a fatty chain comprising, for example, from 8 to 18 carbonatoms, it being possible for the number of ethylene oxide or propyleneoxide groups to range, for example, from 2 to 200 and for the number ofglycerol groups to range, for example, from 2 to 30. Mention may also bemade of copolymers of ethylene oxide and of propylene oxide, condensatesof ethylene oxide and of propylene oxide with fatty alcohols;polyethoxylated fatty amides preferably having from 2 to 30 mol ofethylene oxide and their momoethanolamine and diethanolaminederivatives, polyglycerolated fatty amides, for example, comprising onaverage from 1 to 5, and such as from 1.5 to 4, glycerol groups;polyethoxylated fatty amines such as those containing from 2 to 30 molof ethylene oxide; oxyethylenated fatty acid esters of sorbitan havingfrom 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose, fattyacid esters of polyethylene glycol, alkylpolyglycosides,N-alkylglucamine derivatives, amine oxides such as (C₁₀-C₁₄)alkylamineoxides or N-acylaminopropylmorpholine oxides.

The amphoteric surfactants can be chosen, for example, from aliphaticsecondary and tertiary amine derivatives in which the aliphatic radicalis chosen from linear and branched chains comprising from 8 to 22 carbonatoms and comprising at least one water-soluble anionic group (forexample carboxylate, sulphonate, sulphate, phosphate or phosphonate);mention may also be made of (C₈-C₂₀)alkylbetaines, sulphobetaines,(C₈-C₂₀)alkylamido(C₁-C₆)alkylbetaines or(C₈-C₂₀)alkylamido(C₁-C₆)alkylsulphobetaines. Among the aminederivatives, mention may be made of the products sold under the nameMiranol, as described, for example, in U.S. Pat. Nos. 2,528,378 and2,781,354 and having the structures of:R₂—CON HCH₂CH₂—N⁺(R₃)(R₄)(CH₂COO⁻⁾   (VI)in which: R₂ is chosen from alkyl radicals derived from an acid R₂—COOHpresent in hydrolysed coconut oil, and heptyl, nonyl and undecylradicals, R₃ is a β-hydroxyethyl group and R₄ is a carboxymethyl group;and ofR₅—CONHCH₂CH₂—N(B)(C)   (VII)wherein B represents —CH₂CH₂OX′, C represents —(CH₂)_(z)—Y′, with z=1 or2, X′ is chosen from the —CH₂CH₂—COOH group and a hydrogen atom, Y′ ischosen from —COOH and —CH₂—CHOH—SO₃H radicals, R₅ is chosen from alkylradicals of an acid R₅—COOH present in coconut oil or in hydrolysedlinseed oil, alkyl radicals, such as C₇, C₉, C₁₁ and C₁₃ alkyl radicals,a C₁₇ alkyl radical and its iso form, and unsaturated C₁₇ radical. Thesecompounds are classified in the CTFA dictionary, 5th edition, 1993,under the names disodium cocoamphodiacetate, disodiumlauroamphodiacetate, disodium caprylamphodiacetate, disodiumcapryloamphodiacetate, disodium cocoamphodipropionate, disodiumlauroamphodipropionate, disodium caprylamphodipropionate, disodiumcapryloarnphodipropionate, lauroamphodipropionic acid, andcocoamphodipropionic acid. Salts of diethyl aminopropyl cocoaspartamidcan be also used.

The cationic surfactants may be chosen from: A) the quaternary ammoniumsalts of general formula (VIII) below:

wherein X⁻ is an anion chosen from halides (chloride, bromide andiodide), (C₂-C₆)alkyl sulphates, such as methyl sulphate, phosphates,alkyl and alkylaryl sulphonates, and anions derived from organic acids,such as acetate and lactate, and

-   i) the radicals R₁ to R₃, which may be identical or different, are    chosen from linear and branched aliphatic radicals comprising from 1    to 4 carbon atoms, and aromatic radicals such as aryl and alkylaryl.    The aliphatic radicals can comprise at least one hetero atom such as    oxygen, nitrogen, sulphur and halogens. The aliphatic radicals are    chosen, for example, from alkyl, alkoxy and alkylamide radicals,-   R₄ is chosen from linear and branched alkyl radicals comprising from    16 to 30 carbon atoms.

The cationic surfactant is, for example, a behenyltrimethylammonium salt(for example chloride).

-   ii) the radicals R₁ and R₂, which may be identical or different, are    chosen from linear and branched aliphatic radicals comprising from 1    to 4 carbon atoms, and aromatic radicals such as aryl and alkylaryl.    The aliphatic radicals can comprise at least one hetero atom such as    oxygen, nitrogen, sulphur and halogens. The aliphatic radicals are    chosen, for example, from alkyl, alkoxy, alkylamide and hydroxyalkyl    radicals comprising from about 1 to 4 carbon atoms;-   R₃ and R₄ which may be identical or different, are chosen from    linear and branched alkyl radicals comprising from 12 to 30 carbon    atoms, the said alkyl radicals comprise at least one function chosen    from ester and amide functions.-   R₃ and R₄ are chosen, for example, from    (C₁₂-C₂₂)alkylamido(C₂-C₆)alkyl and (C₁₂-C₂₂)alkylacetate radicals.

The cationic surfactant is, for example, a dicetyldimethyl ammonium salt(for example chloride);

-   B)-the quaternary ammonium salts of imidazolinium, such as that of    formula (IX) below:

in which R₅ is chosen from alkenyl and alkyl radicals comprising from 8to 30 carbon atoms, for example fatty acid derivatives of tallow,

-   R₆ is chosen from a hydrogen atom, C₁-C₄ alkyl radicals and alkenyl    and alkyl radicals comprising from 8 to 30 carbon atoms, R₇ is    chosen from C₁-C₄ alkyl radicals, R₈ is chosen from a hydrogen atom    and C₁-C₄ alkyl radicals, and X⁻ is an anion chosen from halides,    phosphates, acetates, lactates, alkyl sulphates, alkyl sulphonates    and alkylaryl sulphonates.

In one embodiment, R₅ and R₆ are, for example, a mixture of radicalschosen from alkenyl and alkyl radicals comprising from 12 to 21 carbonatoms, such as fatty acid derivatives of tallow, R₇ is methyl and R₈ ishydrogen. Such a product is, for example, Quaternium-27 (CTFA 1997) orQuaternium-83 (CTFA 1997), which are sold under the names “Rewoquat®”W75, W90, W75PG and W75HPG by the company Witco,

-   C)-the diquaternary ammonium salts of formula (X):

in which R₉ is chosen from aliphatic radicals comprising from about 16to 30 carbon atoms,

-   R₁₀, R₁₁, R₁₂, R₁₃ and R₁₄, which may be identical or different, are    chosen from hydrogen and alkyl radicals comprising from 1 to 4    carbon atoms, and-   X⁻ is an anion chosen from halides, acetates, phosphates, nitrates    and methyl sulphates. Such diquaternary ammonium salts, for example,    include propanetallowdiammonium dichloride; and-   D)-the quaternary ammonium salts comprising at least one ester    function, of formula (XI) below:

in which:

-   R15 is chosen from C1-C6 alkyl radicals and C1-C6 hydroxyalkyl and    dihydroxyalkyl radicals; R16 is chosen from: a radical R19C(O)—,    linear and branched, saturated and unsaturated C1-C22    hydrocarbon-based radicals R20, and a hydrogen atom, R18 is chosen    from: a radical R21C(O)—, linear and branched, saturated and    unsaturated C1-C6 hydrocarbon-based radicals R22, and a hydrogen    atom, R17, R19 and R21, which may be identical or different, are    chosen from linear and branched, saturated and unsaturated C7-C21    hydrocarbon-based radicals; n, p and r, which may be identical or    different, are chosen from integers ranging from 2 to 6; y is chosen    from integers ranging from 1 to 10; x and z, which may be identical    or different, are chosen from integers ranging from 0 to 10; X-is an    anion chosen from simple and complex, organic and inorganic anions;    with the proviso that the sum x+y+z is from 1 to 15, that when x is    0, then R16 is R20 and that when z is 0, then R18 is R22.

In one embodiment, the ammonium salts of formula (XV) can be used, inwhich: R15 is chosen from methyl and ethyl radicals, x and y are equalto 1; z is equal to 0 or 1; n, p and r are equal to 2; R16 is chosenfrom: a radical R19C(O)—, methyl, ethyl and C14-C22 hydrocarbon-basedradicals, and a hydrogen atom; R17, R19 and R21, which may be identicalor different, are chosen from linear and branched, saturated andunsaturated C7-C21, hydrocarbon-based radicals; R18 is chosen from: aradical R21 C(O)— and a hydrogen atom. Such compounds are sold, forexample, under the names Dehyquart by the company Cognis, Stepanquat bythe company Stepan, Noxamium by the company Ceca, and Rewoquat WE 18 bythe company Rewo-Witco.

Chelants

According to the present invention the compositions may comprisechelants. Chelants are well known in the art and refer to a molecule ora mixture of different molecules each capable of forming a chelate witha metal ion. Chelants are well known in the art and a non-exhaustivelist thereof can be found in A E Martell & R M Smith, Critical StabilityConstants, Vol. 1, Plenum Press, New York & London (1974) and A EMartell & R D Hancock, Metal Complexes in Aqueous Solution, PlenumPress, New York & London (1996) both incorporated herein by reference.

Examples of chelants suitable for use herein include EDDS(ethylenediaminedisuccinic acid), carboxylic acids (in particularaminocarboxylic acids), phosphonic acids (in particular aminophosphonicacids) and polyphosphoric acids (in particular linear polyphosphoricacids), their salts and derivatives.

Chelants may be incorporated into the composition of the presentinvention as stabilizers and or preservatives. In addition it has alsobeen found that chelants provide hair fibre damage benefits and thusthey may be utilized in order to further improve the hair damage profileof the present invention. Levels of chelants in the present inventionmay be as low as about 0.1%, preferably at least about 0.25%, morepreferably about 0.5% for the most effective chelants such asdiamine-N,N′-dipolyacid and monoamine monoamide-N,N′-dipolyacid chelants(for example EDDS). Less effective chelants will be more preferably usedat levels of at least about 1%, even more preferably above about 2% byweight of the composition, depending of the efficiency of the chelant.Levels as high as about 10% can be used, but above this levelsignificant formulation issues may arise.

Solvents

Suitable solvents for use in the compositions of the present inventioninclude, but are not limited to, water, butoxydiglycol, propyleneglycol, alcohol (denat.), ethoxydiglycol, isopropylalcohol, hexyleneglycol, benzyl alcohol and dipropylene glycol.

Finally, the compositions according to the present invention can beprovided in any usual form, such as for example an aqueous composition,a powder, a gel or an oil-in-water emulsion. A preferred form for thecompositions according to the present invention are thickened solutionscomprising a salt-tolerant thickener or oil-in-water emulsions.

Pre-treatment Compositions

According to one aspect of the method of the present invention the hairis treated with a pre-treatment composition prior to application of thehair colourant or bleaching compositions. Pre-treatment compositionsaccording to the present invention comprise at least one conditioningagent. As used herein, the term “conditioning agent” refers to any agentwhose function is to improve at least one cosmetic property of keratinmaterials such as hair, for example the softness, smoothness,disentangling, feel and static electricity. The at least oneconditioning agent may be soluble or insoluble in water.

Any of the conditioning agents listed herein above as conditioningagents and surfactants may be suitable for use in the pre-treatmentcomposition. Particularly preferable are cationic polymers, siliconematerials, anionic polymers, nonionic polymers, oils and waxes,emulsions made from lamellar liquid crystals and mixtures thereof.

Emulsions made from lamellar liquid crystals which are formed by thecombination of several actives provide improvement in the cosmeticproperties of the composition such as conditioning properties. Thisarises due to the presence of a combination of fatty materials and anemulsifier to from an emulsion. Emulsifiers for use in the aqueouscontinuous phase of the emulsion may include an anionic surfactant,cationic surfactant, amphoteric surfactant, water-soluble polymericsurfactant, water-soluble silicone-containing surfactant, non-ionicsurfactant having an HLB of greater than about 10, or a surfactantsystem capable of forming stabilizing liquid crystals. The nonionicsurfactant preferably has an HLB of at least 12, and more preferably, anHLB value of at least about 15. Surfactants belonging to these classesare listed in McCutcheon's Emulsifiers and Detergents, North Americanand International Editions, MC Publishing Co., Glen Rock N.J., pages235-246 (1993).

The emulsifier for the aqueous phase does not gel the aqueous phase. Theemulsifier however may be capable of forming a stabilizing layer oflamellar liquid crystals. For conciseness, the term “liquid crystalstructure” as used herein, should be taken to also include gel networks,which are solidified liquid crystals. The surfactant system can be asingle surfactant or a blend of surfactants. In some cases, a particularsurfactant cannot form a liquid crystal structure alone, but canparticipate in the formation of liquid crystals in the presence of asecond surfactant.

Exemplary classes of surfactants capable of participating in theformation of a liquid crystal, include but are not limited to specificcationic surfactants, anionic surfactants, nonionic surfactants,quaternary ammonium surfactants and lipid surfactants.

Preferred non-ionic surfactants for the formation of liquid crystals inthe aqueous continuous phase are of the nonionic type and include C16-20fatty alcohols, and C16-20 fatty alcohol ethoxylates with 1 to 30ethylene oxide groups. Specific examples include cetearyl alcohol, cetylalcohol, stearyl alcohol, arachidyl alcohol, oleyl alcohol, cetearethethoxylates with between 10 and 30 ethylene oxide groups, cetethethoxylates with between 10 to 30 ethylene oxide groups, stearethethoxylates with between 10 and 30 ethoxylates, and combinationsthereof. Preferably, C16-22 fatty alcohols are used in combination withC16-22 fatty alcohol ethoxylates at a ratio of between 10:1 to 0.5:1,more preferably between 6:1 and 1:1, and most preferably between 5:1 and1.5:1.

Preferred cationic surfactants contain quaternary ammonium compounds offormula: [R18R19R20R21N]+X—, where R18 is an alkyl or alkenyl grouphaving from about 8 to 22 carbon atoms, R19 and R20 are bothindependently either an alkyl or alkenyl group having from about 8 to 22carbon atoms or alkyl or hydroxyalkyl group having from about 1 to 4carbon atoms, R21 is an alkyl or hydroxyalkyl group having from about 1to 4 carbon atoms, and X— is a salt forming anion (e.g. chloride,bromide, acetate, alkylsulfate).

Advantageously, in order to facilitate formation of liquid crystals, thesurfactant system may also comprise amidoamines of the following generalformula: R22CONH(CH2)m N (R23)2, wherein R22 is a residue of C8 to C24fatty acids, R23 is a C1 to C4 alkyl, and m is an integer from 1 to 4.Preferred amidoamine useful in the present invention includesstearamidopropyldimethylamine, stearamidopropyldiethylamine,stearamidoethyl-diethylamine, stearamidoethyldimethylamine,palmitamidopropyl-dimethylamine, palmitamido-propyldiethylamine,palmitamidoethyl-diethylamine, palmitamido-ethyldimethylamine,behenamidopropyldimethylamine, behenamido-propyldiethylamine,behenamidoethyl-diethylamine, behenamidoethyldimethylamine,arachidamidopropyldimethylamine, arachidamido-propyidiethylamine,arachidamidoethyl-diethylamine, arachidamidoethyl-dimethylamine, andmixtures thereof; more preferably stearamido-propyidimethylamine,stearamidoethyidiethylamine, and mixtures thereof.

More advantageously, the amidoamines are partially quaternized withacids selected from the group consisting of L-glutamic acid, lacticacid, hydrochloric acid, malic acid, succinic acid, acetic acid, fumaricacid, L-glutamicio acid hydrochloride, tartaric acid, and mixturesthereof; preferably L-glutamic acid, lactic acid, hydrochloric acid, andmixtures thereof. Preferably, the mole ratio of amidoamine to acid isfrom about 1:0.3 to about 1:1, more preferably from about 1:0.5 to about1:0.

Polymers suitable as conditioning agents include anionic and nonionicpolymers which may be water-soluble or water insoluble. Suitable anionicpolymers include polymers comprising at least one group derived fromcarboxylic acid, sulphonic acid or phosphoric acid and such as thosehaving a weight-average molecular weight ranging from 500 to 5,000,000,determined, for example, by gel permeation chromatography.

Suitable nonionic polymers include for example, from the followingpolymers:—vinylpyrrolidone homopolymers; copolymers of vinylpyrrolidoneand vinyl acetate; polyalkyloxazolines such as the polyethyloxazolinessold by the company Dow Chemical under the names “Peox 50 000”, “Peox200 000” and “Peox 500 000”; vinyl acetate homopolymers, such as theproduct sold under the name “Appretan EM” by the company Hoechst, andthe product sold under the name “Rhodopas A 012” by the company RhodiaChimie; copolymers of vinyl acetate and acrylic ester, such as theproduct sold under the name “Rhodopas AD 310” by Rhodia Chimie;copolymers of vinyl acetate and ethylene, such as the product sold underthe name “Appretan TV” by the company Hoechst; copolymers of vinylacetate and maleic ester, for example of dibutyl maleate, such as theproduct sold under the name “Appretan MB Extra” by the company Hoechst;copolymers of polyethylene and maleic anhydride; alkyl acrylatehomopolymers and alkyl methacrylate homopolymers, such as the productsold under the name “Micropearl RQ 750” by the company Matsumoto or theproduct sold under the name “Luhydran A 848 S” by the company BASF;acrylic ester copolymers such as copolymers of alkyl acrylates and alkylmethacrylates, such as the products sold by the company Rohm & Haasunder the names “Primal AC-261 K” and “Eudragit NE 30 D”, by the companyBASF under the names “Acronal 601”, “Luhydran LR 8833” and 8845, and bythe company Hoechst under the names “Appretan N 9213” or N 9212;copolymers of acrylonitrile and a nonionic monomer chosen, for example,from butadiene and alkyl (meth)acrylates; mention may be made of theproducts sold under the names “Nipol LX 531 B” by the company NipponZeon and those sold under the name “CJ 0601 B” by the company Rohm &Haas; polyurethanes, such as the products sold under the names “AcrysolRM 1020” and “Acrysol RM 2020” by the company Rohm & Haas, and theproducts “Uraflex XP 401 UZ” and “Uraflex XP 402 UZ” by the company DSMResins; copolymers of alkyl acrylate and urethane, such as the product“8538-33” by the company National Starch; polyamides, such as theproduct “Estapor LO 11” sold by the company Rhodia Chimie; andunmodified and chemically modified nonionic guar gums.

Examples of oils suitable for use as conditioning agents in thepre-treatment method of the present invention include both animal andplant oils, and are for example, chosen from sunflower oil, corn oil,soybean oil, avocado oil, jojoba oil, marrow oil, grapeseed oil, sesameoil, hazelnut oil, fish oils, glyceryl tricaprocaprylate, and plant andanimal oils of formula R₉COOR₁₀ in which R9 is chosen from higher fattyacid residues containing from 7 to 29 carbon atoms and R₁₀ is chosenfrom linear and branched hydrocarbon-based chains containing from 3 to30 carbon atoms, such as alkyl and alkenyl, for example, purcellin oiland liquid jojoba wax.

The waxes are natural (animal or plant) or synthetic substances that aresolid at room temperature (20°-25° C.). They are insoluble in water,soluble in oils and are capable of forming a water-repellent film. Thewaxes are chosen, for example, from carnauba wax, candelilla wax,alfalfa wax, paraffin wax, ozokerite, plant waxes such as olive treewax, rice wax, hydrogenated jojoba wax and absolute waxes of flowerssuch as the essential wax of blackcurrant flower sold by the companyBertin (France), animal waxes such as beeswaxes, and modified beeswaxes(cerabellina). Other waxes or waxy starting materials, which can beused, include, for example, marine waxes such as the product sold by thecompany Sophim under the reference M82, and polyethylene waxes andpolyolefins in general.

The pre-treatment compositions preferably comprise a conditioningagentcomprising an emulsion made from lamellar liquid crystals, morepreferably a fatty alcohol and surfactant emulsion. The pre-treatmentcomposition has a viscosity of from 100 Pa to 300 Pa, preferably from115 Pa to 285 Pa, more preferably from 130 Pa to 250 Pa, most preferablyfrom 160 Pa to 240 Pa. The pre-treatment composition typically comprisesfrom 0.2 to 20%, preferably from 1.0 to 15%, most preferably from 5 to15% of said conditioning agents and preferably has a pH of from 3 to 7,more preferably from pH 4and pH 6.

The pre-treatment composition may further comprise additional adjuncts,which are selected so as not to eliminate or substantially reduce theperformance or shelf stability of the composition. The additionalingredients may include, for example dyes and coloring agents,fragrances; anionic, cationic, non-ionic, amphoteric or zwitterionicsurfactants; buffers, masking fragrances, dispersing agents,stabilizers, cationic polymers, perfumes, non-ionic polymers, anionicpolymers, complex coacervates, complex coacervate capsules, metal salts,lewis acids, buffering agents, particulate thickeners, polymericthickeners, wax thickeners, oils, emollients, humectants, moisturizers,pearlescents, opacifiers, enzymes, suspending agents, antimicrobials,preservatives, proteins, herb and plant extracts, bleach, peroxide,polyols, silicones, solvents, antibodies, pH adjusting agents includingpH buffers, viscosity modifiers, preservatives, viscosity enhancers,gelling agents, chelators, oxidising agents, reducing agents, UVfilters, emulsifying agents, antioxidants, moisturizing and conditioningagents, and other common adjuvants well known to those skilled in theart.

According to the present invention it has been surprisingly found thatthe application of the pre-treatment composition to the hair prior tothe application of the hair colouring or bleaching composition,preferably, without prior rinsing provides a number of unexpectedbenefits. Firstly, the presence of the pre-treatment composition on thehair allows for easier application of the colouring or bleachingcomposition as the hair neither separates too quickly or on the contrarytangles upon application of the composition to the hair particularlyalong the length of the hair. Consequently the compositions can beapplied both more quickly and more effectively. Secondly, thepre-treatment composition also prevents skin staining by the haircolourant compositions. Thirdly, the pre-treatment compositions deliverconditioning benefits which are consumer noticeable already at time ofremoval of the colourant or bleaching composition. Consequently thepre-treatment method reduces the need for a final conditioning stepwhich thus speeds up the time required by the consumer to complete theprocess.

Oxidative hair dye compositions are usually sold in kits comprising, inindividually packaged components such as separate containers, a dyecomponent (also called “dye cream” for emulsions or “dye liquid” forsolutions) comprising the oxidative dye, precursors and alkalizing agentwhich is typically ammonia in a suitable carrier and; a hydrogenperoxide component (also called “hydrogen peroxide cream” for emulsionsor “hydrogen peroxide liquid” for solutions) comprising the oxidizingagent (usually hydrogen peroxide). The consumer mixes the dye componentand hydrogen peroxide component together immediately before use andapplies it onto the hair. The exemplified formulations given in thetables hereinafter illustrate these resulting mixtures.

Similarly, bleaching compositions are also usually sold as a kitcomprising two or three individually packaged components typically intwo or three separate containers. The first component comprises theammonium ion source (e.g. ammonia), the second component comprises theoxidizing agent and the third (optional) component comprises a secondoxidizing agent. The bleaching compositions are obtained by mixing theabove-mentioned compositions immediately before use.

The present invention may be utilized in a variety of packaging anddispensing devices. These dispensing devices can come in the form ofseparate devices which may be used independently or in combination withone another. Typically, the hair colouring or bleaching compositions arecontained within separate single or multi compartment containers so thatthe compositions can be stored separately from one another before use.The compositions are then mixed together by a mixing means and thenapplied to the consumer's hair by an application means.

The most common packaging device which can be used for the presentinvention involves storing the developer in a container such as abottle, tube, aerosol, or a sachet and separately storing the dye lotionin an additional compartment within the developer container or in aseparate container which may be identical such as a dual sachet oraesrosol systems for example or different such as a bottle and tubesystem.

The consumer may mix the developer lotion and the dye lotion by anymeans. This may simply involve the use of a mixing bowl into which thelotions are dispensed and then mixed, preferably using a mixing meanssuch as a tool. Alternatively it may involve the addition of one of thelotions into the container of the other lotion, (typically the dyelotion is added to the developer lotion), followed by manual shaking ormixing with a tool. Another system involves the perforation ordisplacement of a seal located between the separate compartments of thedye and developer lotion within a single container or sachet followed bymanual mixing within the container or in a separate and or additionalcontainer.

An example of such devices are the so called ‘twist and go’ devices.These devices allow the consumer to twist the base of a containerholding the dye which enables a communication port to open that exposesthe base of the bottle holding the dye and the top of the bottle holdingthe developer. The two components are mixed and the consumer dispensesthe product by squeezing the flexible top portion of the bottle fordispensing.

Alternatively more complex devices may be utilised, whereby the lotionsare mixed upon actuation of dispensing. An example of such as a complexsystem is a dual aerosol system e.g. bag-in-can or piston. The dye anddeveloper are stored separately in two aerosol cans within one device, apropellant being used to pressurize the contents of the can or bag incan or piston and a valve providing the control of dispensation. Whenthe consumer actuates the valve, the dye and developer are dispensedsimultaneously out of the cans and are mixed together via a static mixerjust before dispensing the product onto the hair. The ratio of the dyeand developer can be manipulated by the viscosity of the products, thecan pressure, or by altering the flow channel sizes through the valve.Additionally, the product can be foamed and delivered via a mousse form.

Another example of such a complex system utilises a dual piston screwsystem. The dye and the developer are kept in separate piston cylindersystems within the system and when the consumer actuates a button, twoscrews are rotated such that the dual pistons inside pressurize theliquid in the cylinders and thus force the products to move through amixing station and out of the nozzle for dispensing. The ratios of thedye and the developer can be manipulated by the diameter of the cylinderof the package. Additionally, an in line static mixer can be used to aidmixing and such a system can be completely disposable or completelyrefillable.

Yet another system utilises one or more manually actuated pumps. Theproduct may be premixed in a collapsible sachet. When the consumeractuates the pump, the liquid inside the pump is dispensed. As themanually actuated pump returns to the upright position it forces productfrom a collapsible sachet. Alternatively, a dual system can be installedwhereby two sachets and two pumps are used to deliver the dye and thedeveloper lotions to the hair. Alternatively, a single pump connected totwo sachets can deliver the product by incorporating the mixing pointwithin the pump. Another embodiment uses a rigid bottle and a dip tubeto connect the product to the pump system. Finally, a delaminatingbottle can be used in combination with a manually actuated pump wherethe inner layer of the bottle separates from the outer layer of thebottle which forces the contents of the bottle to be emptied.

Typically these complex systems offer the advantage of productapplication independently of the orientation of the product.

The devices described herein above can also be used in combination witha product delivery and or application tool to aid application of theproduct onto the hair. Again these devices may be of a very simplenature such as a nozzle attached to one of the containers or a separateapplicator device such as a comb or brush. Such combs and brushes can beadapted in order to achieve particular effects, whether it be quick andeven coverage or root/hairline touch up, or highlights or streaks.Alternatively, the container or one of the containers may be providedwith a comb attached to or instead of the dispensing nozzle whereby theproduct is dispensed through hollow tines and dispensing apertureslocated in the comb tines. The comb tines may be provided with single ormultiple openings along the tines to improve product application andevenness especially root to tip. Product dispensation can be achieved bymechanical pressure applied to: the container for example delaminatingbottles or any of the mechanisms described hereinabove. The comb may beprovided on the container such as to facilitate easy application and maybe positioned vertically (so called verticomb) or at an angle to allowthe consumer to access all areas. All devices may be designed to haveinter-changeability, so that a range of different tools for hairapplication can be provided to the consumer.

The application devices may also include devices which assist inachieving particular effects such as highlighting such as highlightingcombs, brushes and tools, foils and highlighting caps.

Additional device technology can be used to assist in the penetration ofthe product into the hair. Examples of such technology include heatingdevices, ultraviolet light devices and ultrasound devices.

Method of Use

According to the present invention the method of colouring or bleachinghair comprises after applying the composition to the hair and preferablyworking the mixture for a few minutes (to insure uniform application toall of the hair), the composition is allowed to remain on the hair inorder for the colour to develop for a time period of less than about 20minutes, preferably less than about 15 minutes, more preferably fromabout 5 minutes to about 10 minutes, most preferably for about 10minutes. The consumer then rinses his/her hair thoroughly with tap waterand allows it to dry and or styles the hair as usual. It can be observedthat the hair will have as changed from its original color to thedesired color.

According to an alternative embodiment of the present invention, themethod of colouring and or bleaching the hair is a sequential oxidativehair colouring or hair bleaching method comprising the steps of at leasttwo sequential oxidative hair colour or hair bleaching treatmentswherein the time period between each treatment is from 1 to 60 days,preferably from 1 to 40 days, more preferably from 1 to 28 days, evenmore preferably from 1 to 14 days and most preferably from 1 to 7 days.In such embodiments the time that the composition is retained on headmay be less than about 20 minutes and is preferably less than about 10minutes and most preferably from about 2 minutes to about 5 minutes.

According to another embodiment of the present invention the method ofcolouring or bleaching comprises a pre-treatment step whereby apre-treatment composition comprising at least one conditioning agent isapplied to the hair and without subsequent rinsing, the hair colourantor bleaching composition is then applied. Such a pre-treatmentcomposition would also typically be packaged in a separate container.

When present in the oxidative dye compositions and bleachingcompositions, the optional conditioning agent can be provided in a thirdcontainer. In the latter case, all three compositions can be mixedimmediately before use and applied together, or the content of the thirdcontainer can be applied (after an optional rinse step) as apost-treatment immediately after the oxidative dye composition orbleaching composition resulting from the mixture of the othercontainers.

For the compositions comprising a radical scavenger, the scavenger maybe comprised within the dye component, the hydrogen peroxide component,the pre-treatment composition, if present, or may be comprised as aseparate radical scavenger component, separately packaged. Similarly,for the bleaching composition, the radical scavenger may be comprisedwithin the ammonium ion source component, the oxidising agent component,or the second oxidising agent component, the pre-treatment compositionif present or within a separate radical scavenger component, orcomprised within two or more of the components. Preferably, however theradical scavengers are comprised within the dye component. The radicalscavenger is typically applied to the hair during or after anypre-treatment composition application but prior to the application ofthe hair colourant or bleaching composition. Alternatively the radicalscavenger is mixed with the dye or oxidant component.

In another embodiment of the present invention the kit may comprise aseparate component comprising other sensitive materials such as certaindyes for example dyes cationic azo dyes which are not stable in the maindye component.

The kits described hereinabove are well known in the art and thecomposition in each container can be manufactured utilizing any one ofthe standard approaches, these include a) ‘Oil in water’ process, b)‘Phase Inversion’ process and c) ‘One-pot’ process.

For example, in a ‘One-pot’ process, the polymers and chelants would bepre-dissolved in water, the fatty materials added and then the wholecomposition heated to about 70-80° C. A controlled cooling and optionalshearing process to form the final structured product in the case of anemulsion would then follow. Addition of the materials providing sourceof peroxymonocarbonate ions, radical scavengers and ammonia, andoptionally solvents, dyes and pH trimming complete the making process ofthe dye cream.

In the case of a liquid solution comprising acrylate polymers, thesewould be formulated into the hydrogen peroxide component. The glycolsolvents and fatty components are formulated into the dye component. Astructured product is formed when the dye and hydrogen peroxidecomponents are mixed together prior to use of the composition, resultingfrom deprotonation of the polymer acrylic acid groups as the pH rises,yielding a polymeric micro-gel. Further details on the manufacture ofthese two-part aqueous composition for coloring hair, which forms a gelon mixing of the two parts can be found in U.S. Pat. No. 5,376,146,Casperson et al. and U.S. Pat. No. 5,393,305, Cohen et al.

The composition of the present invention can also be formulated as2-part aqueous compositions comprising polyetherpolyurethane asthickening agent (such as Aculyn ® 46) as described in U.S. Pat. Nos.6,156,076 and 6,106,578.

EXAMPLES

The following examples illustrate oxidative dye compositions accordingto the present invention and methods of manufacture thereof.

Examples of Emulsion Formulations 1-10

Formulation Ingredient 1 2 3 4 5 6 7 8 9 10 Sodium sulphite 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 0.1 0.1 Ascorbic Acid 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 Ammonium Carbonate 3.0 6.0 2.0 — 4.0 8.0 2.0 — 4.0 6.0Potassium Hydrogen — — 1.5 2.0 — — 2.0 2.0 — — Carbonate AmmoniumAcetate — — — 2.0 — — — 2.0 — — Ceteareth-25 1.0 — — — — — — 1.0 1.0 1.0Steareth-100 — 1.0 1.0 — — — — — — — Sodium Palmytoyl — — — — 1.0 — — —— — Sarcosinate Sodium Carboxymethyl — — — 1.0 — — — — — — LaurylGlucoside Sodium Lauryl Sulfate — — — — — 1.0 — — — — BehentrimoniumChlorid — — — — — — 1.0 — — — Cetyl Alcohol 1.6 — 2   1.5 1.5 1.5 2.52.5 1.6 1.6 Stearyl Alcohol 3.3 — 2   1.5 1.5 1.5 2.5 2.5 3.3 3.3Steareth-2 — 5   1   — — — — — — — Sodium Benzoate 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 Phenoxyethanol 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 EDTA (tetrasodium salt) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1Sodium Glycinate 2.0 5.0 3.0 1.0 — — — — — 3.0 Glutamic Acid — — — — —6.0 2.0 — — — Glycine — — — 1.0 2.0 Glucosamine — — — — — — 2.0 4.0 4.03.0 Para-phenylene-diamine 0.8 0.5 0.6 0.5 0.8 0.8 0.5 0.6 0.5 0.8Para-aminophenol 0.2 0.3 0.2 0.1 0.2 0.2 0.3 0.2 0.1 0.2Meta-aminophenol 1.0 0.5 1.0 0.6 1.0 1.0 0.5 1.0 0.6 1.0 Resorcinol 1.61.2 1.6 0.8 1.6 1.6 1.2 1.6 0.8 1.6 Hydrogen Peroxide 8.6 8.6 8.6 12.9 17   17   17   10.7  10.7  10.7  (35% active) Amodimethicone 1.5 — — — —— — — 1.0 — (Belsil ADM1100) Trimethylsilylamo- — 0.5 — — — — — 2.0 — —dimethicone (SF1708) Polyquaternium-22 — — 2.0 — 0.1 — — — — — (Merquat295) Polyquaternium-37 & — — — 0.5 0.1 — — — — — Mineral oil (SalcareSC95) Polyquaternium 10 — — — — — 0.2 0.2 — — — (Polymer JR30M)Dicetyldimonium Chloric — — — — — — — — 0.2 — Xanthan gum 0.1 0.5 — —0.2 — — — — — Cetyl hydroxyethyl — — 0.8 — — — — — — — Cellulose(Natrosol 330C Plus) pH adjust to pH 9.0 qs qs qs qs qs qs qs qs qs qsWater qs qs qs qs qs qs qs qs qs qs

Examples of Emulsion Formulations 11-20

Formulation Ingredient 11 12 13 14 15 16 17 18 19 20 Sodium sulphite 0.10.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Erythorbic Acid 0.2 0.2 0.2 0.2 0.20.2 0.2 0.2 0.2 0.2 Ammonium Carbonate 3.0 6.0 2.0 — 4.0 8.0 2.0 — 4.06.0 Potassium Hydrogen — — 1.5 2.0 — — 2.0 2.0 — — Carbonate AmmoniumAcetate — — — 2.0 — — — 2.0 — — Crodafos ® CES 2.0 3.0 4.0 3.0 3.0 3.03.0 3.0 3.0 3.0 EDTA (tetrasodium salt) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 EDDS (disodium salt) — — — — — 2.5 — — — — Sodium Glycinate 3.05.0 2.0 1.0 — — — — — 3.0 Glutamic Acid — — — — — 6.0 2.0 — — — Glycine— — — 1.0 2.0 — — — — — Glucosamine — — — — — — 2.0 4.0 4.0 3.0Dipropylene glycol 5.0 1.0 5.0 4.0 5.0 5.0 3.0 4.0 3.0 5.0Para-phenylene-diamine 0.8  0.006 0.6 0.5 0.8 0.8 0.5 0.6 0.5 0.8Para-aminophenol 0.2 — — 0.1 0.2 0.2 0.3 0.2 0.1 0.2 Meta-aminophenol1.0 — — 0.6 1.0 1.0 0.5 1.0 0.6 1.0 Resorcinol 1.6  0.012 1.6 0.8 1.61.6 1.2 1.6 0.8 1.6 1-Naphthol — — 0.2 — — — — — — — Hydrogen Peroxide8.6 12.8  8.6 12.9  17   17   17   10.7  10.7  10.7  (35% active)Amodimethicone 1.5 — — — — — — — 1.0 — (Belsil ADM1100)Trimethylsilylamo- — — — — — — — 2.0 — — dimethicone (SF1708)Polyquaternium-22 — — 2.0 — 0.5 — — — — — (Merquat 295)Polyquaternium-37 & — — — 0.5 0.1 — — — — — Mineral oil (Salcare SC95)Styrene-PVP copolymer 0.2 1.0 0.7 1.0 2.0  2.00 2.0 0.6 0.6 0.6 (Antara430) Dicetyldimonium Chloric — — — — — — — — 0.2 — Xanthan gum 0.1 — —0.2 — — — — — — Succinoglycan — — — — 0.2 0.5 — — — — Carbomer — — — — —— 1.0 0.5 — — Acrylates/C10-30 Alkyl — — — — — — — 0.5 — — AcrylateCrosspolymer Hydroxyethyl cellulose — — — — — — — — 0.5 — HydroxypropylStarch — — — — — — — — — 2.0 Phosphate pH adjust to pH 9.0 qs qs qs qsqs qs qs qs qs qs Water qs qs qs qs qs qs qs qs qs qs

Examples of Thickened Aqueous Solution Formulations 1-10

Formulation Ingredient 1 2 3 4 5 6 7 8 9 10 Sodium sulphite 0.1 0.1 0.10.1 0.1 0.1 0.1 0.1 0.1 0.1 Ascorbic Acid 0.1 0.1 0.1 0.1 0.1 0.1 0.10.1 0.1 0.1 Citric Acid 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 1.0 AmmoniumCarbonate 3.0 6.0 2.0 — 4.0 8.0 2.0 — 4.0 6.0 Potassium Hydrogen — — 1.52.0 — — 2.0 2.0 — — Carbonate Ammonium Acetate — — — 2.0 — — — 2.0 — —Oleth 10 1.0 1.0 1.0 1.0 — — — — — — Oleth 2 0.8 0.8 0.8 0.8 — — — — — —Oleic Acid 0.9 0.9 0.9 0.9 — — — — — — Cocamide DEA 3.0 3.0 3.0 3.0 — —— — — — EDTA(tetrasodium salt) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1Sodium Glycinate 2.0 5.0 3.0 1.0 — — — — — — Glutaminc Acid — — — — —6.0 2.0 — — — Glycine — — — 1.0 2.0 — — — — — Glucosamine — — — — — —2.0 4.0 4.0 3.0 Para-phenylene Diamine 0.8 0.5 0.6 0.5 0.8 0.8 0.5 0.60.5 0.8 Para-aminophenol 0.2 0.3 0.2 0.1 0.2 0.2 0.3 0.2 0.1 0.2Meta-aminophenol 1.0 0.5 1.0 0.6 1.0 1.0 0.5 1.0 0.6 1.0 Resorcinol 1.61.2 1.6 0.8 1.6 1.6 1.2 1.6 0.8 1.6 Hydrogen Peroxide 8.6 8.6 8.6 13  17   17   17   10.7  10.7  10.7  (35% active) Polyquaternium-22 (Merqu —— — — 0.5 — — — — — 295) Polyquaternium-37 & Mine — — — — 0.1 — 0.5 — —— (Salcare SC95) Amodimethicone — — — — — 1.0 — — — — (Belsil ADM1100)Acrylates Copolymer 2.4 2.4 2.4 2.4 — — — — — — (Aculyn ® 33A) AcrylatesSteareth-20 0.5 0.5 — 1.0 — — — — — — Methacrylate Copolymer (Aculyn ®22) Xanthan gum — — — — — 1.0 — — — — Succinoglycan — — — — 0.8 — — — —— Carbomer — — — — — — 2.0 — — Acrylates/C10-30 Alkyl — — — — — — — 2.0— — Acrylate Crosspolymer Hydroxyethyl cellulose — — — — — — — — 2.0 —Hydroxypropyl Starch — — — — — — — — — 2.0 Phosphate Propylene Glycol8.2 8.2 8.2 8.2 8.0 8.0 8.0 8.0 8.0 8.0 Ethoxy Diglycol 4.2 4.2 4.2 4.2— — — — — — pH adjust to pH 9.0 qs qs qs qs qs qs qs qs qs qs Water qsqs qs qs qs qs qs qs qs qsPre-treatment Composition Examples

Pre-treatment compositions 1-6 below were made by heating the water to80° C. then adding the glutamic acid and stearamidopropyl dimethylamineand fatty alcohols, EDTA and benzyl alcohol and mixing. The mixture isthen cooled to below the phase transition, the additional ingredientsadded and then cooled to 30° C. The mixture is them milled using aSilverson SL2 for 3 minutes.

Composition 1 2 3 4 5 6 Cetyl alcohol 1.05 2.8 2.45 1.4 1.75 1.75Stearyl alcohol 1.89 5.04 4.41 2.52 3.15 3.15 Stearamido- 0.84 2.24 1.961.12 1.40 1.40 propyl dimethyamine L-Glutamic 0.27 0.72 0.63 0.36 0.450.45 acid Tetrasodium 0.03 0.08 0.07 0.04 0.05 0.05 EDTA (87%) Benzylalcohol 0.12 0.32 0.28 0.16 0.20 0.20 Kathon CG 0.009 0.024 0.021 0.0120.015 0.015 silicone 1.50 4.00 3.50 2.00 2.50 2.50 Demineralised qs qsqs qs qs qs water Rheology 115 355 280 175 225 225 850 s⁻¹

An AR 500 rotational rheometer (TA Instruments Ltd., Leatherhead, SurreyKT22 7UQ, UK) is used to determine the viscosity of the pre-treatmentcompositions. The determination is performed at 26.7° C., with the 4 cm2° steel cone measuring system set with a 50 μm (micron) gap and isperformed via the programmed application of a shear rate from 0.5 to1000 1/s over a 1 minute time period with 10 data points recorded perdecade. These data are used to create a shear rate vs. shear stresscurve for the material. The value obtained on the plotted graphs at 850s⁻¹ is recorded.

The exemplified pre-treatment compositions described hereinabove may beapplied to wet or dry (preferably dry) hair. Immediately prior to use,the dye component and the oxidant component are mixed together. Theresultant mixture is then applied to the hair. If the consumer has notcoloured their hair previously, or if they are changing their haircolour from the previous colour, the mixture is applied to the whole ofthe hair by massaging the product into the hair, starting at the rootsand ending at the tips (a so called ‘full head application’). Once theapplication is complete a further amount of time between 6-15 minutes(preferably 10 minutes) is allowed for the colour to develop. Theproduct is then rinsed from the hair with warm water until no more dyewill rinse out. A conditioner product can then optionally be applied.

If the consumer is colouring with the same colour (a so called ‘roottouch up application’) then after the dye component and oxidantcomponent are mixed, a portion of the mixture is applied first to theroots of the hair. Once application to the roots is complete, a periodof 5-9 mins is allowed for the colour to develop. The remaining mixtureis then applied to the rest of the hair and a further period (afterapplication is complete) of between 1 and 10 minutes is allowed for thecolour to develop. Preferably the total amount of time allowed fordevelopment is 10 minutes or less. After the development time iscomplete the product is rinsed from the hair as described in the fullhead application description hereinabove.

If a pretreatment composition is being used, this composition is appliedfirst to the dry hair. The pretreatment composition remains on the hairwithout rinsing whilst the ‘full head application’ or ‘root touch upapplication’ protocols described above are used. In the instance wherethe pretreatment is an effective conditioner it may be possible for theconsumer to omit the final separate conditioning treatment from theregime—this simplifies the procedure and makes it faster overall.

All documents cited in the Detailed Description of the Invention are, inrelevant part, incorporated herein by reference; the citation of anydocument is not to be construed as an admission that it is prior artwith respect to the present invention. To the extent that any meaning ordefinition of a term in this written document conflicts with any meaningor definition of the term in a document incorporated by reference, themeaning or definition assigned to the term in this written documentshall govern.

While particular embodiments of the present invention have beenillustrated and described, it would be obvious to those skilled in theart that various other changes and modifications can be made withoutdeparting from the spirit and scope of the invention. It is thereforeintended to cover in the appended claims all such changes andmodifications that are the scope of this invention.

1. A method of oxidatively colouring or bleaching hair in less thanabout 20 minutes comprising the steps of: i) providing a compositioncomprising at least one source of peroxymonocarbonate ions and at leastone source of alkalizing agent, wherein said composition has a pH offrom about 7.5 to about 9.5 ii) applying said composition on the hairand maintaining said composition on the hair for a time period of lessthan about 20 minutes, and subsequently iii) rinsing said compositionfrom the hair.
 2. A method of sequential oxidative hair colouring orhair bleaching comprising the steps of at least two sequential oxidativehair colour or hair bleaching treatments wherein the time period betweeneach treatment is from about 1 to about 60 days and wherein eachtreatment comprises the steps of i) providing a composition comprisingat least one source of peroxymonocarbonate ions and at least one sourceof alkalizing agent, wherein said composition has a pH of from about 7.5to about 9.5, and then ii) applying said composition to the hair andretaining said composition on the hair for a time period of less thanabout 20 minutes and subsequently iii) rinsing said composition from thehair.
 3. A method of colouring or bleaching hair according to claim 1,wherein said method further comprises a first pre-treatment step,wherein a pre-treatment composition comprising at least one conditioningagent is applied to the hair.
 4. A method of colouring or bleaching hairaccording to claim 3, wherein said pre-treatment composition is notrinsed from the hair prior to the next step.
 5. A method of colouring orbleaching hair according to claim 1, wherein said composition ismaintained on the hair for a time period of less than about 15 minutes.6. A method of colouring or bleaching hair according to claim 1, whereinsaid source of peroxymonocarbonate ions comprises at least one source ofhydrogen peroxide and at least one source of carbonate ions, carbamateions, hydrocarbonate ions, or mixtures thereof.
 7. A method of colouringor bleaching hair according to claim 1, wherein said at least one sourceof alkalizing agent is a source of ammonium ions.
 8. A method ofcolouring or bleaching hair according to claim 6, wherein saidcomposition comprises: b. from about 0.1% to about 10% by weight of saidat least one source hydrogen peroxide; c. from about 0.1% to about 10%by weight of said at least one source of alkalizing agent; and d. fromabout 0.1% to about 15% by weight of said at least one source ofcarbonate ions, carbamate ions, hydrocarbonate ions, or mixturesthereof.
 9. A method of colouring or bleaching hair according to claim1, wherein said composition further comprises at least one oxidative dyeand or at least one direct dye.
 10. A method of colouring or bleachinghair according to claim 1, wherein said composition further comprises aradical scavenger.
 11. A method of colouring or bleaching hair accordingto claim 1, wherein said composition further comprises a chelatingagent.